CN1784389A - Pyrimidine compounds and pests controlling composition containing the same - Google Patents

Pyrimidine compounds and pests controlling composition containing the same Download PDF

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CN1784389A
CN1784389A CNA2004800124738A CN200480012473A CN1784389A CN 1784389 A CN1784389 A CN 1784389A CN A2004800124738 A CNA2004800124738 A CN A2004800124738A CN 200480012473 A CN200480012473 A CN 200480012473A CN 1784389 A CN1784389 A CN 1784389A
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compound
mixture
pyrimidine
oxygen base
alkyl
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CN100378082C (en
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水野肇
真锅明夫
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/34—One oxygen atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The present invention relates to a pyrimidine compound of the formula (I):wherein R 1< represents a hydrogen atom, halogen atom or C1-C4 alkyl; R 2 represents C3-C7 alkynyloxy; R 3 represents a hydrogen atom, halogen atom or C1-C3 alkyl; X represents C4-C7 polymethylene, in which a CH2#191-CH2#191 may be replaced with a CH=CH, optionally substituted with at least one substituent selected from the group consisting of halogen atoms, trifluoromethyl and C1-C4 alkyls. This pyrimidine compound has an excellent activity of controlling pests.

Description

Pyrimidine compound and the pests controlling composition that contains this pyrimidine compound
Technical field
The present invention relates to pyrimidine compound and the pests controlling composition that contains this pyrimidine compound.
Background technology
Past has been used all cpds for the prevention and control of plant diseases, pest control.Known compound with pyrimidine ring is pest control (WO 02/024663) effectively.And known compound with the pyrimidine ring that is replaced by piperidino-(1-position only) is also effective.
Disclosure of the Invention
Target of the present invention provide effective prevention and elimination of disease and pests pyrimidine compound, have this pyrimidine compound as the pests controlling composition of effective constituent and the method for prevention and elimination of disease and pests.
Promptly the invention provides the pyrimidine compound (being called The compounds of this invention hereinafter) of formula (I):
Wherein, R 1Expression hydrogen atom, halogen atom or C1-C4 alkyl; R 2Expression C3-C7 alkynyloxy group; R 3Expression hydrogen atom, halogen atom or C1-C3 alkyl; X represents the C4-C7 polymethylene, wherein can replace CH with CH=CH 2-CH 2, described polymethylene is selected from optional replacement of substituting group of halogen atom, trifluoromethyl and C1-C4 alkyl by at least one; Contain the pests controlling composition of The compounds of this invention as effective constituent; The method of prevention and elimination of disease and pests, described method comprises the habitat that the The compounds of this invention of significant quantity is applied to insect or insect.
Invention embodiment
In this manual, " sec " represents secondary, and " tert " represents uncle.The expression mode of " C3-C7 " for example in " C3-C7 alkynyloxy group ", is meant the number of total carbon atom in the substituting group." C3-C7 alkynyloxy group " is meant that total carbon atom number is 3-7 in the alkynyloxy group.
In this manual,
R 1Represented halogen atom comprises, for example, and fluorine atom and chlorine atom;
R 1Represented C1-C4 alkyl for example comprises methyl, ethyl, propyl group, sec.-propyl, butyl and isobutyl-;
R 2Represented C3-C7 alkynyloxy group comprises for example C3-C7 alkynyloxy group, wherein in the alkynyl three key between 2 and 3 carbon (being called the C3-C72-alkynyloxy group hereinafter), the C3-C72-alkynyloxy group comprises for example 2-third alkynyloxy group, 2-butyne oxygen base, 1-methyl-2-butyne oxygen base, valerylene oxygen base, 4,4-dimethyl-valerylene oxygen base, 1-methyl-2-third alkynyloxy group and 1,1-dimethyl-2-third alkynyloxy group;
R 3Represented halogen atom comprises for example fluorine atom and chlorine atom;
R 3Represented C1-C3 alkyl comprises for example methyl and ethyl.
In the represented C4-C7 polymethylene of X, wherein can replace CH with CH=CH 2-CH 2, described polymethylene can be by the optional replacement of halogen atom, trifluoromethyl and C1-C4 alkyl; Halogen atom comprises fluorine atom, chlorine atom and bromine atoms; The C1-C4 alkyl comprises methyl, ethyl, propyl group, sec.-propyl, isobutyl-, sec-butyl and the tertiary butyl.
In the represented C4-C7 polymethylene of X, wherein can replace CH with CH=CH 2-CH 2, described polymethylene can be replaced CH with at least one optional replacement of substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl with CH=CH in the C4-C7 polymethylene 2-CH 2, comprise tetramethylene, pentamethylene, hexamethylene, heptamethylene and 2-amylene-1, the 5-subunit.
The C4-C7 polymethylene that X is represented wherein can be replaced CH with CH=CH 2-CH 2, described polymethylene is comprised the optional C4-C7 polymethylene that replaces of substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one by at least one optional replacement of substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl; With the linear alkenylene of the optional C4-C7 that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one.Comprised the C4-C7 polymethylene of for example C4-C7 polymethylene, halogen atom replacement, the C4-C7 polymethylene that trifluoromethyl replaces, the C4-C7 polymethylene that the C1-C4 alkyl replaces by at least one optional C4-C7 polymethylene that replaces of substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl; More specifically, comprise tetramethylene, 1-methyl tetramethylene, 2-methyl tetramethylene, 1-ethyl tetramethylene, 1-propyl group tetramethylene, 1-sec.-propyl tetramethylene, 1-(tertiary butyl) tetramethylene, 2-ethyl tetramethylene, 1,4-dimethyl tetramethylene, 2,3-dimethyl tetramethylene, 2,2-dimethyl tetramethylene, 2-fluorine tetramethylene, 2-(trifluoromethyl) tetramethylene, 3-(trifluoromethyl) tetramethylene, 1, the 5-pentylidene, the 1-methyl isophthalic acid, the 5-pentylidene, the 2-methyl isophthalic acid, the 5-pentylidene, the 3-methyl isophthalic acid, the 5-pentylidene, 1-ethyl-1, the 5-pentylidene, 2-ethyl-pentamethylene, 1-propyl group-pentamethylene, 2-propyl group-1, the 5-pentylidene, 3-propyl group-1, the 5-pentylidene, 1-sec.-propyl-pentamethylene, 2-sec.-propyl-pentamethylene, 3-sec.-propyl-1, the 5-pentylidene, 1-(tertiary butyl)-1, the 5-pentylidene, 2-(tertiary butyl)-pentamethylene, 3-(tertiary butyl)-pentamethylene, 1-(sec-butyl)-1, the 5-pentylidene, 2-(sec-butyl)-1, the 5-pentylidene, 1,5-dimethyl-pentamethylene, 1,3-dimethyl-1, the 5-pentylidene, 1,4-dimethyl-pentamethylene, 2,4-dimethyl-1, the 5-pentylidene, 1,1-dimethyl-pentamethylene, 2,2-dimethyl-1, the 5-pentylidene, 3,3-dimethyl-pentamethylene, 2-ethyl-5-methyl isophthalic acid, the 5-pentylidene, 2-ethyl-4-methyl isophthalic acid, the 5-pentylidene, 2,4-diethyl-pentamethylene, 1,2-dimethyl-1, the 5-pentylidene, 2,2,4-trimethylammonium-1, the 5-pentylidene, 1,2,4,5-tetramethyl--1, the 5-pentylidene, 2,2,4,4-tetramethyl--1, the 5-pentylidene, 2-fluoro-1, the 5-pentylidene, 2-chloro-pentamethylene, 2-bromo-pentamethylene, 3-fluoro-1, the 5-pentylidene, 3-chloro-1, the 5-pentylidene, 3-bromo-pentamethylene, 2,2-two fluoro-1, the 5-pentylidene, 3,3-two fluoro-pentamethylene, 2-fluoro-2-methyl isophthalic acid, the 5-pentylidene, 1-(trifluoromethyl)-1, the 5-pentylidene, 2-(trifluoromethyl)-1, the 5-pentylidene, 3-(trifluoromethyl)-pentamethylene, hexamethylene, the 1-methyl isophthalic acid, the 6-hexylidene, the 2-methyl isophthalic acid, the 6-hexylidene, the 3-methyl isophthalic acid, the 6-hexylidene, the 4-methyl isophthalic acid, the 6-hexylidene, 1-ethyl-1, the 6-hexylidene, 2-ethyl-1, the 6-hexylidene, 3-ethyl-hexamethylene, 1-propyl group-hexamethylene, 2-propyl group-1, the 6-hexylidene, 3-propyl group-1, the 6-hexylidene, 1-sec.-propyl-hexamethylene, 2-sec.-propyl-hexamethylene, 3-sec.-propyl-1, the 6-hexylidene, 1-(tertiary butyl)-1, the 6-hexylidene, 1-isobutyl--hexamethylene, 1-(trifluoromethyl)-hexamethylene, 1,4-dimethyl-1, the 6-hexylidene, 1,5-dimethyl-hexamethylene, 1,6-dimethyl-1, the 6-hexylidene, 2,5-dimethyl-hexamethylene and heptamethylene.
Be selected from halogen atom by at least one, the linear alkenylene of the optional C4-C7 that replaces of the substituting group of trifluoromethyl and C1-C4 alkyl, for example, 2-butylene-1, the 4-subunit, 2-methyl-2-butene-1, the 4-subunit, 2,3-dimethyl-2-butylene-1, the 4-subunit, 2-amylene-1, the 5-subunit, 1-ethyl-2-amylene-1, the 5-subunit, 2-methyl-2-amylene-1, the 5-subunit, 2-ethyl-2-amylene-1, the 5-subunit, 4-methyl-2-amylene-1, the 5-subunit, 5-methyl-2-amylene-1, the 5-subunit, 5-ethyl-2-amylene-1, the 5-subunit, 2,4-dimethyl-2-amylene-1, the 5-subunit, 2-hexene-1, the 6-subunit, 1-methyl-2-hexene-1, the 6-subunit, 1-ethyl-2-hexene-1, the 6-subunit, 2-methyl-2-hexene-1, the 6-subunit, 6-ethyl-2-hexene-1, the 6-subunit, 2,5-dimethyl-2-hexene-1, the 6-subunit, 3-hexene-1, the 6-subunit, 2-heptene-1,7-subunit and 3-heptene-1,7-subunit.
The embodiment of The compounds of this invention comprises for example following compound:
1) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom or C1-C4 alkyl;
2) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom;
3) R in the pyrimidine compound, its Chinese style (I) 2Be the C3-C72-alkynyloxy group;
4) R in the pyrimidine compound, its Chinese style (I) 2Be 2-butyne oxygen base or valerylene oxygen base;
5) R in the pyrimidine compound, its Chinese style (I) 3Be hydrogen atom;
6) R in the pyrimidine compound, its Chinese style (I) 2Be halogen atom;
7) R in the pyrimidine compound, its Chinese style (I) 2Be fluorine atom;
8) X is the optional C4-C7 polymethylene that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one in the pyrimidine compound, its Chinese style (I);
9) X is by the optional C4-C7 polymethylene that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl in the pyrimidine compound, its Chinese style (I);
10) X is the C4-C7 polymethylene in the pyrimidine compound, its Chinese style (I);
11) the C4-C7 polymethylene of X for being replaced in the pyrimidine compound, its Chinese style (I) by halogen atom;
12) the C4-C7 polymethylene of X for being replaced in the pyrimidine compound, its Chinese style (I) by trifluoromethyl;
13) the C4-C7 polymethylene of X for being replaced in the pyrimidine compound, its Chinese style (I) by the C1-C4 alkyl;
14) X is by the optional C4-C7 polymethylene that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl in the pyrimidine compound, its Chinese style (I);
15) X replaces for the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one is optional in the pyrimidine compound, its Chinese style (I) tetrem support (tetraethylene) or pentamethylene;
16) X is the linear alkenylene of the optional C4-C7 that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one in the pyrimidine compound, its Chinese style (I);
17) X is the optional tetramethylene that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one in the pyrimidine compound, its Chinese style (I);
18) X is the optional pentamethylene that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one in the pyrimidine compound, its Chinese style (I);
19) X is the optional hexamethylene that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one in the pyrimidine compound, its Chinese style (I);
20) X is by the optional C4-C7 polymethylene that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl in the pyrimidine compound, its Chinese style (I);
21) X is by the optional tetramethylene that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl in the pyrimidine compound, its Chinese style (I);
22) X is by the optional pentamethylene that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl in the pyrimidine compound, its Chinese style (I);
23) X is by the optional hexamethylene that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl in the pyrimidine compound, its Chinese style (I);
24) X is by the optional tetramethylene that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl in the pyrimidine compound, its Chinese style (I);
25) X is by the optional pentamethylene that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl in the pyrimidine compound, its Chinese style (I);
26) X is by the optional hexamethylene that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl in the pyrimidine compound, its Chinese style (I);
27) X is a tetramethylene in the pyrimidine compound as described below, its Chinese style (I);
28) X is a pentamethylene in the pyrimidine compound as described below, its Chinese style (I);
Figure A20048001247300092
29) X is a hexamethylene in the pyrimidine compound as described below, its Chinese style (I);
Figure A20048001247300093
30) X is a heptamethylene in the pyrimidine compound as described below, its Chinese style (I);
Figure A20048001247300094
31) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom or C1-C4 alkyl, and X is the optional C4-C7 polymethylene that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one;
32) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom or C1-C4 alkyl, and X is by the optional C4-C7 polymethylene that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl;
33) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom or C1-C4 alkyl, and X supports or pentamethylene for the optional tetrem that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one;
34) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom or C1-C4 alkyl, and X is the linear thiazolinyl of the optional C4-C7 that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one;
35) R in the pyrimidine compound, its Chinese style (I) 2Be 2-butyne oxygen base or valerylene oxygen base, and X is the optional C4-C7 polymethylene that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one;
36) R in the pyrimidine compound, its Chinese style (I) 2Be 2-butyne oxygen base or valerylene oxygen base, and X is by the optional C4-C7 polymethylene that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl;
37) R in the pyrimidine compound, its Chinese style (I) 2Be 2-butyne oxygen base or valerylene oxygen base, and X supports or pentamethylene for the optional tetrem that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one;
38) R in the pyrimidine compound, its Chinese style (I) 2Be 2-butyne oxygen base or valerylene oxygen base, and X is the linear alkenylene of the optional C4-C7 that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one;
39) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom or C1-C4 alkyl, R 2Be 2-butyne oxygen base or valerylene oxygen base, and X is the optional C4-C7 polymethylene that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one;
40) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom or C1-C4 alkyl, R 2Be 2-butyne oxygen base or valerylene oxygen base, and X is by the optional C4-C7 polymethylene that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl;
41) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom or C1-C4 alkyl, R 2Be 2-butyne oxygen base or valerylene oxygen base, and X supports or pentamethylene for the optional tetrem that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one;
42) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom or C1-C4 alkyl, R 2Be 2-butyne oxygen base or valerylene oxygen base, and X is the linear alkenylene of the optional C4-C7 that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one;
43) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 3Be hydrogen atom;
44) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 3Be halogen atom;
45) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 3Be fluorine atom;
46) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 2Be C3-C72-alkynyloxy group, R 3Be hydrogen atom;
47) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 2Be C3-C72-alkynyloxy group, R 3Be halogen atom;
48) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 2Be C3-C72-alkynyloxy group, R 3Be fluorine atom;
49) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 2Be C3-C72-alkynyloxy group, R 3Be hydrogen atom, and X is the optional C3-C81 that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one, 5-pentylidene;
50) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 2Be C3-C72-alkynyloxy group, R 3Be halogen atom, and X is the optional C3-C81 that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one, 5-pentylidene;
51) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 2Be C3-C72-alkynyloxy group, R 3Be fluorine atom, and X is the optional C3-C81 that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one, 5-pentylidene;
52) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 2Be C3-C72-alkynyloxy group, R 3Be hydrogen atom, and X is the optional C3-C81 that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one, 6-hexylidene;
53) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 2Be C3-C72-alkynyloxy group, R 3Be halogen atom, and X is the optional C3-C81 that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one, 6-hexylidene;
54) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 2Be C3-C72-alkynyloxy group, R 3Be fluorine atom, and X is the optional C3-C81 that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one, 6-hexylidene;
55) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 2Be C3-C72-alkynyloxy group, R 3Be hydrogen atom, and X is by the optional C3-C81 that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl, 5-pentylidene;
56) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 2Be C3-C72-alkynyloxy group, R 3Be halogen atom, and X is by the optional C3-C81 that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl, 5-pentylidene;
57) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 2Be C3-C72-alkynyloxy group, R 3Be fluorine atom, and X is by the optional C3-C81 that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl, 5-pentylidene;
58) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 2Be C3-C72-alkynyloxy group, R 3Be hydrogen atom, and X is by the optional C3-C81 that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl, 6-hexylidene;
59) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 2Be C3-C72-alkynyloxy group, R 3Be halogen atom, and X is by the optional C3-C81 that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl, 6-hexylidene;
60) R in the pyrimidine compound, its Chinese style (I) 1Be hydrogen atom, R 2Be C3-C72-alkynyloxy group, R 3Be fluorine atom, and X is by the optional C3-C81 that replaces of halogen atom, trifluoromethyl or C1-C4 alkyl, 6-hexylidene;
The following describes production method of the present invention.
For example can produce The compounds of this invention by the production method 1 and 2 that describes below.
Production method 1
In the presence of alkali, by making the reaction of formula (II) compound and formula (III) compound, can production formula (I) compound.
Figure A20048001247300121
R wherein 1, R 2, R 3As above define with X.
This reaction is carried out in solvent usually.
Enumerated employed solvent in the reaction at this, for example, ether such as tetrahydrofuran (THF), diethyl ether, t-butyl methyl ether, glycol dimethyl ether and 1,4-diox, acid amides such as N, dinethylformamide, nitrile such as acetonitrile, sulfoxide such as methyl-sulphoxide, hydrocarbon such as hexane, aromatic hydrocarbons such as benzene and toluene, and their mixture.
Enumerated employed alkali in the reaction at this, for example, alkalimetal hydride such as sodium hydride and potassium hydride KH, carbonate such as salt of wormwood, alkali metal alcoholates such as potassium tert.-butoxide and sodium tert-butoxide.
Based on 1 mole of formula (II) compound, then the consumption of formula (III) compound is generally the 1-2 mole, and the consumption of alkali is generally the 1-2 mole.
Between 0-80 ℃, the scope in reaction times is usually between 0.5-12 hour usually for the scope of temperature of reaction.
Finish after the reaction, by as reaction mixture is extracted into organic solvent, drying and enrichment step, separate type (I) compound.Can be further purified isolating formula (I) compound through chromatography and recrystallization etc.
Production method 2
By making formula (IV) compound and formula V compound or its salt (as the hydrochloride of formula V compound) reaction, can production formula (I) compound.
Figure A20048001247300131
R wherein 1, R 2, R 3As above define with X.
This reaction is carried out in solvent usually, chooses wantonly in the presence of alkali and carries out.
Enumerated employed solvent in the reaction at this, for example, ether such as tetrahydrofuran (THF), diethyl ether, t-butyl methyl ether, glycol dimethyl ether and 1,4-diox, acid amides such as N, dinethylformamide, nitrile such as acetonitrile, pure as methyl alcohol and ethanol, hydrocarbon such as hexane, aromatic hydrocarbons such as benzene and toluene, and their mixture.
Enumerated employed alkali in the reaction at this, for example, alkalimetal hydride such as sodium hydride and potassium hydride KH, carbonate such as salt of wormwood, tertiary amine such as triethylamine and ethyl diisopropylamine.
Based on 1 mole of formula (IV) compound, then the consumption of formula V compound is generally the 1-3 mole.When carrying out under being reflected at the alkali existence, based on 1 mole of formula (IV) compound, the consumption of alkali is generally the 1-4 mole.
Between 0-150 ℃, the scope in reaction times is usually between 0.1-48 hour usually for the scope of temperature of reaction.
After reaction is finished, by following steps separate type (I) compound:
(i) reaction mixture is extracted into organic solvent, dry and concentrated;
(ii) direct concentrated reaction mixture.
Can be further purified isolating formula (I) compound through chromatography and recrystallization etc.
Next the production method of The compounds of this invention intermediate will be described.
With reference to production method 1
By making the hydrochloride reaction of formula (VI) compound and formula V compound or its salt such as formula V compound, can production formula (II) compound.
Figure A20048001247300141
Wherein, R 1, R 2, R 3As above define with X.
This reaction is carried out in solvent usually, chooses wantonly in the presence of alkali and carries out.
Enumerated employed solvent in the reaction at this, for example, ether such as tetrahydrofuran (THF), diethyl ether, t-butyl methyl ether, glycol dimethyl ether and 1,4-diox, acid amides such as N, dinethylformamide, nitrile such as acetonitrile, alcohol is as methyl alcohol and ethanol, hydrocarbon such as hexane, aromatic hydrocarbons such as benzene and toluene, sulfoxide such as methyl-sulphoxide, and their mixture.
Enumerated employed alkali in the reaction at this, for example, alkalimetal hydride such as sodium hydride and potassium hydride KH, carbonate such as salt of wormwood, alkali metal hydroxide such as potassium tert.-butoxide and sodium tert-butoxide.
Based on 1 mole of formula V compound, then the consumption of formula (VI) compound is generally the 1-3 mole.When carrying out under being reflected at the alkali existence, based on 1 mole of formula V compound, the consumption of alkali is generally the 1-4 mole.
Between 0-150 ℃, the scope in reaction times is usually between 0.1-48 hour usually for the scope of temperature of reaction.
After reaction is finished, by following steps separate type (II) compound:
(i) reaction mixture is extracted into organic solvent, dry and concentrated;
(ii) direct concentrated reaction mixture.
Can be further purified isolating formula (II) compound through chromatography and recrystallization etc.
Formula (II) compound comprises, for example Yi Xia compound:
The compound of formula (II), wherein X is the C4-C7 polymethylene;
Formula (II ') compound:
Figure A20048001247300151
Wherein, R 1Expression hydrogen atom, halogen atom or C1-C4 alkyl; R 3Expression hydrogen atom, halogen atom or C1-C3 alkyl; X 3Expression C4-C7 polymethylene wherein can be replaced CH with CH=CH 2-CH 2, described polymethylene is selected from optional replacement of substituting group of halogen atom, trifluoromethyl and C1-C4 alkyl by at least one;
The compound of formula (II '), wherein X 3Be the optional C4-C7 polymethylene that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one;
The compound of formula (II '), wherein X 3For chosen wantonly the C4-C7 polymethylene that replaces by halogen atom; The compound of formula (II '), wherein X 3For chosen wantonly the C4-C7 polymethylene that replaces by trifluoromethyl; The compound of formula (II '), wherein X 3For chosen wantonly the C4-C7 polymethylene that replaces by the C1-C4 alkyl.
With reference to production method 2
By formula (VI) compound and formula (III) compound are reacted in the presence of alkali, can production formula (IV) compound.
Figure A20048001247300161
Wherein, R 1, R 2, R 3As above define with X.
This reaction is carried out in solvent usually, chooses wantonly in the presence of alkali and carries out.
Enumerated employed solvent in the reaction at this, for example, ether such as tetrahydrofuran (THF), diethyl ether, t-butyl methyl ether, glycol dimethyl ether and 1,4-diox, acid amides such as N, dinethylformamide, nitrile such as acetonitrile, hydrocarbon such as hexane, aromatic hydrocarbons such as benzene and toluene, sulfoxide such as methyl-sulphoxide, and their mixture.
Enumerated employed alkali in the reaction at this, for example, alkalimetal hydride such as sodium hydride and potassium hydride KH, carbonate such as salt of wormwood, alkali metal hydroxide such as potassium tert.-butoxide and sodium tert-butoxide.
Based on 1 mole of formula (IV) compound, the consumption of formula (III) compound is generally the 1-2 mole, and the consumption of alkali is generally the 1-2 mole.
Between-20～80 ℃, the scope in reaction times is usually between 0.5-12 hour usually for the scope of temperature of reaction.
Finish after the reaction, by as reaction mixture is extracted into organic solvent, drying and enrichment step, separate type (IV) compound.
Can be further purified isolating formula (IV) compound through chromatography and recrystallization etc.
Formula (IV) compound comprises for example following compound:
The compound of formula (IV), wherein R 1Be hydrogen atom or C1-C4 alkyl;
The compound of formula (II), wherein R 1Be hydrogen atom;
The compound of formula (IV), wherein R 2Be 2-butyne oxygen base or valerylene oxygen base.
With reference to production method 3
Formula (V ') compound for example can be through following flow process from the production of formula (IX) compound.
Figure A20048001247300171
Wherein, X 1Expression is selected from the optional C3-C6 polymethylene that replaces of substituting group of halogen atom, trifluoromethyl and C1-C4 alkyl by at least one.
Process 3-1
At solvent Chinese style (VII) compound and azanol reaction, can production formula (VIII) compound.
This reaction is carried out in solvent usually, chooses wantonly in the presence of alkali and carries out.
Enumerated employed solvent in the reaction at this, for example, ether such as tetrahydrofuran (THF), diethyl ether, t-butyl methyl ether, glycol dimethyl ether and 1, the 4-diox, acid amides such as N, dinethylformamide, pure as methyl alcohol and ethanol, water, and their mixture.
Enumerated employed alkali in the reaction at this, for example, mineral alkali such as sodium hydroxide and potassium hydroxide, tertiary amine such as triethylamine, nitrogenous aromatic substance such as pyridine.
Based on 1 mole of formula (VII) compound, the consumption of azanol or its salt is generally the 1-3 mole, and the consumption of alkali is generally the 1-5 mole.
Between 0-80 ℃, the scope in reaction times is usually between 1-24 hour usually for the scope of temperature of reaction.
Finish after the reaction, by as reaction mixture is extracted into organic solvent, drying and enrichment step, separate type (VIII) compound.
Can be further purified isolating formula (VIII) compound through chromatography and recrystallization etc.
Formula (IX) compound is disclosed compound, for example at Synthesis, and (1980), 222-223 page or leaf; Or J.Am.Chem.Soc., (1983), 105,2381-2843 page or leaf; Maybe can be by following process production.
Process 3-2
Through type (VIII) compound reacts in the presence of rearrangement reaction reagent, can production formula (IX) compound.
This reaction is carried out in solvent usually.
Enumerated employed solvent in the reaction at this, for example, acid amides such as N, dinethylformamide, aromatic hydrocarbons such as toluene and benzene, and their mixture.
As rearrangement reaction reagent, the muriate such as the phosphoryl chloride of phosphorus, the muriate of sulphur such as thionyl chloride, and Tripyrophosphoric acid have been enumerated at this.
Based on 1 mole of formula (VIII) compound, the consumption of rearrangement reaction reagent is generally 0.1 mole to excessive.
Between 0-150 ℃, the scope in reaction times is usually between 0.1-48 hour usually for the scope of temperature of reaction.
Finish after the reaction, by as reaction mixture is extracted into organic solvent, drying and enrichment step, separate type (VIII) compound.
Can be further purified isolating formula (VIII) compound through chromatography and recrystallization etc.
Formula (V ') compound is disclosed compound, for example is disclosed in J.Am.Chem.Soc., (1983), 105,2381-2843 page or leaf or J.Heterocyclic.Chem., (1980) 17, in 603 pages; Or by following process production.
Process 3-3
Through type (IX) compound and reduction reagent react can production formula (V ') compounds.
This reaction is carried out in solvent usually.
Enumerated employed solvent, for example ether such as tetrahydrofuran (THF) and diethyl ether in the reaction at this.
As going back original reagent, the hydride such as the lithium aluminum hydride of aluminium have been enumerated at this.
Based on 1 mole of formula (IX) compound, the consumption of going back original reagent is the 0.5-6 mole.
Between 0-120 ℃, the scope in reaction times is usually between 1-24 hour usually for the scope of temperature of reaction.
After reaction is finished, by following steps separate type (V ') compound:
(i) successively water, 15% aqueous sodium hydroxide solution and water are poured into reaction mixture, collection is gone into organic solvent, and drying concentrates; Distillation when needing;
(ii) successively water, 15% aqueous sodium hydroxide solution and water are poured into reaction mixture, collection is gone into organic solvent, drying, the hydrochloride by stirring collection type (V ') compound in the presence of hydrogenchloride or hydrochloric acid.
With reference to production method 4
(V ") compound for example can be by following flow process from the production of formula (IX) compound for formula.
Figure A20048001247300191
Wherein, X 2Expression is selected from the optional C2-C5 polymethylene that replaces of substituting group of halogen atom, trifluoromethyl and C1-C4 alkyl by at least one.
Process 4-1
Through type (X) compound and urea reaction can production formula (XI) compounds.
This reaction is carried out in the presence of solvent usually.
Based on 1 mole of formula (X) compound, the consumption of urea be 10 moles to excessive.
Between 50-170 ℃, the scope in reaction times is usually between 1-24 hour usually for the scope of temperature of reaction.
Finish after the reaction, by as reaction mixture is extracted into organic solvent, drying and enrichment step, separate type (XI) compound.
Be further purified isolating formula (XI) compound through chromatography and recrystallization etc.
Process 4-2
Through type (XI) compound and reductive agent reaction can be produced (V ") compound.
This reaction is carried out in solvent usually.
Enumerated employed solvent, for example ether such as tetrahydrofuran (THF) and diethyl ether in the reaction at this.
As employed reductive agent in the reaction, the hydride such as the lithium aluminum hydride of aluminium have been enumerated at this.
Based on 1 mole of formula (XI) compound, the consumption of reductive agent is generally the 1-6 mole.
Between 0-120 ℃, the scope in reaction times is usually between 1-24 hour usually for the scope of temperature of reaction.
After reaction is finished, separate the formula V compound by following steps:
(i) successively water, 15% aqueous sodium hydroxide solution and water are poured into reaction mixture, collection is gone into organic solvent, and drying concentrates; Distillation when needing;
(ii) successively water, 15% aqueous sodium hydroxide solution and water are poured into reaction mixture, collection is gone into organic solvent, and drying passes through to stir the collection type (hydrochloride of V ") compound in the presence of hydrogenchloride or hydrochloric acid.
Next will show specific examples of the present invention.
Figure A20048001247300201
1) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be 2-third alkynyloxy group, R 3Be hydrogen atom, X is a group that is selected from following group (A).
Group (A):
Tetramethylene, 1-methyl tetramethylene, 1-ethyl tetramethylene, 1-propyl group tetramethylene, 1-sec.-propyl tetramethylene, 1-(tertiary butyl) tetramethylene, 1,4-dimethyl tetramethylene, 2-(trifluoromethyl) tetramethylene, 3-(trifluoromethyl) tetramethylene, 1, the 5-pentylidene, the 1-methyl isophthalic acid, the 5-pentylidene, the 2-methyl isophthalic acid, the 5-pentylidene, the 3-methyl isophthalic acid, the 5-pentylidene, 1-ethyl-1, the 5-pentylidene, 2-ethyl-1, the 5-pentylidene, 1-propyl group-1, the 5-pentylidene, 2-propyl group-1, the 5-pentylidene, 3-propyl group-1, the 5-pentylidene, 3-sec.-propyl-1, the 5-pentylidene, 1-(tertiary butyl)-1, the 5-pentylidene, 3-(tertiary butyl)-1, the 5-pentylidene, 1-(sec-butyl)-1, the 5-pentylidene, 1,5-dimethyl-pentamethylene, 1,3-dimethyl-1, the 5-pentylidene, 1,4-dimethyl-pentamethylene, 2,2-dimethyl-1, the 5-pentylidene, 3,3-dimethyl-pentamethylene, 2-ethyl-5-methyl isophthalic acid, the 5-pentylidene, 2-fluoro-1, the 5-pentylidene, 3-fluoro-1, the 5-pentylidene, 2,2-two fluoro-pentamethylene, 3,3-two fluoro-1, the 5-pentylidene, 1-(trifluoromethyl)-pentamethylene, 2-(trifluoromethyl)-pentamethylene, 3-(trifluoromethyl)-1, the 5-pentylidene, 1, the 6-hexylidene, the 1-methyl isophthalic acid, the 6-hexylidene, the 2-methyl isophthalic acid, the 6-hexylidene, the 3-methyl isophthalic acid, the 6-hexylidene, 1-ethyl-1, the 6-hexylidene, 2-ethyl-hexamethylene, 3-ethyl-hexamethylene, 1-propyl group-1, the 6-hexylidene, 1-sec.-propyl-1, the 6-hexylidene, 1-(tertiary butyl)-hexamethylene, 1-isobutyl--hexamethylene, 1,4-dimethyl-1, the 6-hexylidene, 1,5-dimethyl-hexamethylene, 1,6-dimethyl-1, the 6-hexylidene, 2,5-dimethyl-hexamethylene, 1-(trifluoromethyl)-1, the 6-hexylidene, heptamethylene, 2-amylene-1,5-subunit and 2,4-dimethyl-2-amylene-1,5-subunit.
2) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be 2-butyne oxygen base, R 3Be methyl, X is a group that is selected from following group (B).
Group (B):
Tetramethylene, 1-methyl tetramethylene, 1-ethyl tetramethylene, 1,4-dimethyl tetramethylene, 2-(trifluoromethyl) tetramethylene, 3-(trifluoromethyl) tetramethylene, 1, the 5-pentylidene, 1-methyl 1, the 5-pentylidene, the 2-methyl isophthalic acid, the 5-pentylidene, the 3-methyl isophthalic acid, the 5-pentylidene, 1-ethyl-1, the 5-pentylidene, 2-ethyl-1, the 5-pentylidene, 1,5-dimethyl-pentamethylene, 1,3-dimethyl-1, the 5-pentylidene, 1,4-dimethyl-pentamethylene, 2,2-dimethyl-1, the 5-pentylidene, 3,3-dimethyl-pentamethylene, 2-ethyl-5-methyl isophthalic acid, the 5-pentylidene, 1-(trifluoromethyl)-1, the 5-pentylidene, 2-(trifluoromethyl)-1, the 5-pentylidene, 3-(trifluoromethyl)-pentamethylene, hexamethylene, the 1-methyl isophthalic acid, the 6-hexylidene, the 2-methyl isophthalic acid, the 6-hexylidene, the 3-methyl isophthalic acid, the 6-hexylidene, 1-ethyl-hexamethylene, 2-ethyl-1, the 6-hexylidene, 3-ethyl-1, the 6-hexylidene, 1-(trifluoromethyl)-hexamethylene, heptamethylene, 2-amylene-1,5-subunit and 2,4-dimethyl-2-amylene-1, the 5-subunit.
3) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be 2-third alkynyloxy group, R 3Be fluorine atom, X is a group that is selected from group (A).
4) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be 2-third alkynyloxy group, R 3Be the chlorine atom, X is one and is selected from group (B) group.
5) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be 1-methyl-2-third alkynyloxy group, R 3Be the chlorine atom, X is a group that is selected from group (B).
6) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be valerylene oxygen base, R 3Be hydrogen atom, X is a group that is selected from following group (C).
Group (C):
Tetramethylene, 1-methyl tetramethylene, 2-methyl tetramethylene, 1-ethyl tetramethylene, 1-propyl group tetramethylene, 1-sec.-propyl tetramethylene, 1-(tertiary butyl) tetramethylene, 2-ethyl tetramethylene, 1,4-dimethyl tetramethylene, 2,3-dimethyl tetramethylene, 2,2-dimethyl tetramethylene, 2-fluorine tetramethylene, 2-(trifluoromethyl) tetramethylene, 3-(trifluoromethyl) tetramethylene, 1, the 5-pentylidene, the 1-methyl isophthalic acid, the 5-pentylidene, the 2-methyl isophthalic acid, the 5-pentylidene, the 3-methyl isophthalic acid, the 5-pentylidene, 1-ethyl-1, the 5-pentylidene, 2-ethyl-1, the 5-pentylidene, 1-propyl group-1, the 5-pentylidene, 2-propyl group-1, the 5-pentylidene, 3-propyl group-1, the 5-pentylidene, 1-sec.-propyl-1, the 5-pentylidene, 2-sec.-propyl-1, the 5-pentylidene, 3-sec.-propyl-1, the 5-pentylidene, 1-(tertiary butyl)-1, the 5-pentylidene, 2-(tertiary butyl)-1, the 5-pentylidene, 3-(tertiary butyl)-1, the 5-pentylidene, 1-(sec-butyl)-1, the 5-pentylidene, 2-(sec-butyl)-1, the 5-pentylidene, 1,5-dimethyl-1, the 5-pentylidene, 1,3-dimethyl-1, the 5-pentylidene, 1,4-dimethyl-1, the 5-pentylidene, 2,4-dimethyl-1, the 5-pentylidene, 1,1-dimethyl-1, the 5-pentylidene, 2,2-dimethyl-1, the 5-pentylidene, 3,3-dimethyl-1, the 5-pentylidene, 2-ethyl-4-methyl isophthalic acid, the 5-pentylidene, 2-ethyl-5-methyl isophthalic acid, the 5-pentylidene, 2,4-diethyl-1, the 5-pentylidene, 2-fluoro-1, the 5-pentylidene, 2-chloro-1, the 5-pentylidene, 2-bromo-1, the 5-pentylidene, 3-fluoro-pentamethylene, 3-chloro-pentamethylene, 3-bromo-1, the 5-pentylidene, 2,2-two fluoro-pentamethylene, 3,3-two fluoro-1, the 5-pentylidene, 2-fluoro-2-methyl isophthalic acid, the 5-pentylidene, 1-(trifluoromethyl)-pentamethylene, 2-(trifluoromethyl)-pentamethylene, 3-(trifluoromethyl)-1, the 5-pentylidene, 1, the 6-hexylidene, the 1-methyl isophthalic acid, the 6-hexylidene, the 2-methyl isophthalic acid, the 6-hexylidene, the 3-methyl isophthalic acid, the 6-hexylidene, 1-ethyl-1, the 6-hexylidene, 2-ethyl-hexamethylene, 3-ethyl-hexamethylene, 1-propyl group-1, the 6-hexylidene, 2-propyl group-1, the 6-hexylidene, 3-propyl group-hexamethylene, 1-sec.-propyl-hexamethylene, 2-sec.-propyl-1, the 6-hexylidene, 3-sec.-propyl-1, the 6-hexylidene, 1-(tertiary butyl)-hexamethylene, 1-isobutyl--hexamethylene, 1,4-dimethyl-1, the 6-hexylidene, 1,5-dimethyl-hexamethylene, 1,6-dimethyl-1, the 6-hexylidene, 2,5-dimethyl-hexamethylene, 1-(trifluoromethyl)-1, the 6-hexylidene, heptamethylene, 2-amylene-1,5-subunit and 2,4-dimethyl-2-amylene-1,5-subunit.
7) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be valerylene oxygen base, R 3Be methyl, X is a group that is selected from above-mentioned group (B).
8) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be valerylene oxygen base, R 3Be fluorine atom, X is a group that is selected from above-mentioned group (C).
9) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be valerylene oxygen base, R 3Be the chlorine atom, X is a group that is selected from above-mentioned group (A).
10) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be 2-butyne oxygen base, R 3Be hydrogen atom, X is a group that is selected from above-mentioned group (C).
11) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be 2-butyne oxygen base, R 3Be fluorine atom, X is a group that is selected from above-mentioned group (C).
12) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be 2-butyne oxygen base, R 3Be the chlorine atom, X is a group that is selected from above-mentioned group (A).
13) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be 1-methyl-2-third alkynyloxy group, R 3Be hydrogen atom, X is a group that is selected from above-mentioned group (A).
14) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be 1-methyl-2-third alkynyloxy group, R 3Be fluorine atom, X is a group that is selected from above-mentioned group (A).
15) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be 1-methyl-2-butyne oxygen base, R 3Be hydrogen atom, X is a group that is selected from above-mentioned group (A).
16) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be 1-methyl-2-butyne oxygen base, R 3Be fluorine atom, X is a group that is selected from above-mentioned group (A).
17) pyrimidine compound, wherein R 1Be hydrogen atom, R 2Be 1-methyl-2-butyne oxygen base, R 3Be the chlorine atom, X is a group that is selected from above-mentioned group (B).
The compounds of this invention comprises arthropods (as insect, acarid) and nematode to its activated insect, and specific examples is as follows:
Hemiptera (Hemiptera):
Delphacidae (Delphacidae), for example small brown rice planthopper (Laodelphax striatellus), brown paddy plant hopper (Nilaparvata lugens), white backed planthopper (Sogatella furcifera) etc.,
Angle top Cicadidae (Deltocephalidae), for example rice green leafhopper (Nephotettixcincticeps), nephotettix bipunctatus (Nephotettix virescens) etc.,
Aphidiadae (Aphididae), for example cotten aphid (Aphis gossypii), black peach aphid (Myzus persicae) etc.,
Pentatomiddae (Pentatomidae) is for example spent the green stinkbug in angle (Nezara antennata), beans honeybee coried (Riptortus clavetus) etc.,
Aleyrodidae (Aleyrodidae), for example greenhouse whitefly (Trialeurodes vaporariorum), Bemisia argentifolii (Bemisia argentifolii) etc.,
A red-spotted lizard section (Coccidae), for example red kidney Aspidiotus a red-spotted lizard (Aonidiella aurantii), Sheng Qiongsikang armored scale (Comstockaspis perniciosa), citrus point armored scale (Unaspis citri), red ceroplastes floridensis (Ceroplastes rubens), Australia icerya purchasi (Icerya purchasi) etc.
Tingidae (Tingidae),
Psyllidae (Psyllidae) etc.;
Lepidopteran (Lepidoptera):
Pyralidae (Pyralidae), the for example wild snout moth's larva (Notarcha derogata) of striped rice borer (Chilo suppressalis), cnaphalocrocis medinalls guenee (Cnaphalocrocis medinalis), lap leaf, India paddy phycitid (Plodia interpunctella) etc.
Noctuidae (Noctuidae), for example prodenia litura (Spodoptera litura), mythimna separata (Pseudaletia separata), Thoricoplusia spp., real noctuid (Heliothis spp.), noctuid (Helicoverpa spp.) etc.,
Sulfur butterfly (Pieridae), small white (Pieris rapae) etc. for example,
Tortricidae (Tortricidae) is for example rolled up moth (Adoxophyes spp.), oriental fruit months (Grapholita molesta), Pericarpium Mali pumilae steinernema (Cydia pomonella) etc.,
Moth fruit moth section (Carposinidae), peach fruit moth (Carposina niponensis) etc. for example,
Lyonetid section (Lyonetiidae), lyonetid (Lyonetia spp.) etc. for example,
Lymantriidae (Lymantriidae), for example poison moth (Lymantria spp.), pornography and drug moth (Euproctis spp.) etc.,
Yponomeutidae (Yponomeutidae), small cabbage moth (Plutella xylostella) etc. for example,
Gelechidae (Gelechiidae), Pectinophora gossypiella (Pectinophora gossypiella) etc. for example,
Arctiidae (Arctiidae), fall webworms (Hyphantria cunea) etc. for example,
Rain moth section (Tineidae), for example Tinea translucens, curtain rain moth (Tineolabisselliella) etc.;
Diptera (Diptera):
Calicedae, for example culex pipiens pollens (Culex pipiens pallens), Culex tritaeniorhynchus (Culex tritaeniorhynchus), Culex quinquefasciatus (Culex quinquefasciatus) etc.,
Yellow-fever mosquito (Aedes spp.), for example Aedes aegypti (Aedes aegypti), text of an annotated book yellow-fever mosquito (Aedesalbopictus) etc.,
Anopheles (Anopheles), Anopheles sinensis (Anopheless sinensis) etc. for example,
Chironomidae (Chironomidae),
Nuscidae (Muscidae), for example housefly (Musca domestica), false stable fly (Muscinastabulans) etc.,
Calliphoridae (Calliphoridae),
Flesh flies (Sarcophagidae),
Latrine fly section (Fanniidae),
Anthomyiidae (Anthomyiidae), for example fly (Delia antigua) etc. is planted on delia platura (Delia platura), green onion ground,
Tephritidae (Tephritidae),
Drosophilidae (Drosophilidae),
Moth files (Psychodidae),
Tabanidae (Tabanidae),
Simulidae (Simuliidae),
The Nuscidae of stinging (Stomoxyidae),
Agromyzidae (Agromyzidae) etc.;
Coleoptera (Coleoptera):
South America chrysomelid (Diabrotica spp.), for example corn root leaf A (Diabroticavirgifera), Diabrotica undecimpunctata howardi etc.,
Scarabaeidae (Scarabaeidae), for example bronze different beetle (Anomala cuprea), polychrome different beetle (Anomala rufocuprea) etc.,
Curculionidae (Curculionidae), for example sitophilus zea-mais (sitophilus zeamais), rice water resemble (Lissorhoptrus oryzophilus), Callosobruchus chinensis (Callosobruchus chinesis) etc.,
TRenebrionidae (Tenebrionidae), for example bloom first (Tenebrio molitor), red flour beetle (Tribolium castaneum) etc.,
Chrysomelidae (Chrysomelidae), for example aulacophora femoralis (Aulacophora femoralis), Phyllotreta striolata (Phyllotreta striolata), colorado potato beetles (Leptinotarsadecemlineata) etc.,
Anobiidae (Anobiidae),
Ladybug (Epilachna spp.), potato ladybug (Epilachnavigintioctopunctata) etc. for example,
Lyctidae (Lyctidae),
Bostrichidae (Bostrychidae),
Cerambycidae (Cerambycidae),
Paederus fuscipes Curtis (Paederus fuscipes);
Blattodea (Blattodea):
Groton bug (Blattella germanica), Peroplaneta fluligginosa (Periplaneta fuliginosa), periplaneta americana (Periplaneta americana), the big Lian of foxiness (Periplaneta brunnea), oriental cockroach (Blatta orientalis) etc.;
Thysanoptera (Thysanoptera):
Palm thrips (Thrips palmi), onion thrips (Thrips tabaci), Frankliniella occidentalis (Frankliniella occidentalis) etc.;
Hymenoptera (Hymenoptera):
Formicidae (Formicidae), for example MonomoriumMayr (Monomorium pharaonis), Vespidae (Vespidae), Bethylidae (bethylid wasps), Tenthredinidae (Tenthredinidae), for example Japanese cabbage sawfly (Athalia japonica) etc.;
Orthoptera (Orthoptera):
Gryllotalpidae (Gryllotalpidae), sword angle locust section (Acrididae) etc.;
Siphonaptera (Aphaniptera):
Cat flea (Ctenocephalides felis), dog flea (Ctenocephalides canis), Pulex irritans (Pulex irritans), mouse flea (Xenopsylla cheopts);
Anoplura (Anoplura)
Head louse (Pediculus humanus capitis), crab louse (Phthirus pubis), haematopinus eurysternus (Haematopinus eurysternus), Dalmalinia ovis etc.;
Isoptera (Isoptera):
Eastern subterranean termite (Reticulitermes speratus), Taiwan formosanes (Coptotermesformosanus) etc.;
Acarina (Acarina):
Tetranychidae (Tetranychidae), for example Tetranychus urticae (Tetranychus urticae), citrus red mite (crm) (Panonychus citri), unguiculus mite (Oligonychus spp.) etc.,
Eriophyidae (Eriophyidae), tangerine peronium goitre mite (Aculops pelekassi) etc. for example,
Tarsonemidae (Tarsonemidae), Polyphagotarsonemus latus Banks (Polyphagotarsonemus latus) etc. for example,
Tenuipalpidae (Tenuipalpidae),
Du Ke mite section (Tuckerellidae),
Hard tick section (Ixodidae), for example haemaphysalis longicornis (Haemaphysalis longicornis), haemaphysalis flava (Haemaphysalis flava), dermacentor taiwanensis (Dermacentor taiwanicus), ixodes ovatus (Ixodes ovatus), ixodes persulcatus (Ixodes persulcatus), boophilus microplus (Boophilus microplus), brown dog tick (Rhipicephalus sanguineus) etc.
Tyroglyphidae (Acaridae), tyrophagus putrescentiae (Tyrophagus putrescentiae) etc. for example,
Epidermis mite section (Epidermoptidae), for example dust mite (Dermatophagoidesfarinae), dermatophagoides pteronyssinus (Dermatophagoides ptrenyssnus) etc.,
Cheyletidae (Cheyletidae), for example common cheyletid mite (Cheyletus eruditus), Malacca cheyletid mite (Cheyletus malaccensis), Cheyletus moorei etc.,
Dermanyssidae (Dermanyssidae) etc.
Nematode (Nematodes):
Coffee pratylenchus (Pratylenchus coffeae), Pratylenchus fallax, soy bean cyst roundworm (Heterodera glycines), Globadera rostochiensis, northern root knot nematode (Meloidogyne hapla), Meloidogyne incognita (Meloidogyne incognita) etc.
Pests controlling composition of the present invention contains The compounds of this invention and inert support.Generally speaking, it in case of necessity, adds tensio-active agent and other preparation and prepares with auxiliary material by mixing The compounds of this invention and carrier such as solid carrier, liquid vehicle, carrier gas and/or poisoning bait.Described preparation for example comprises oily solution, emulsion, preparation, wettable powder, granule, pulvis, microcapsule etc. can flow.Convertible these preparations are used for the sheet poison bait.In pests controlling composition of the present invention, The compounds of this invention content is generally 0.01-95% weight.
Enumerated employed solid carrier in the preparation at this, for example well as clay fines or particle (kaolin, diatomite, synthetic hydrated silicon oxide, wilkinite, Fubasami soil, acid clay etc.), talcum powder, potter's clay, other inorganic materials (sericite, quartz, sulphur, gac, lime carbonate and hydrated SiO 2 etc.), chemical fertilizer (ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and ammonium chloride) etc.; Enumerated at this that employed liquid vehicle comprises in preparation, water for example, alcohol (methyl alcohol, ethanol etc.), ketone (acetone, methylethylketone etc.), aromatic hydrocarbons (benzene, toluene, dimethylbenzene, ethylbenzene, methylnaphthalene etc.), aliphatic hydrocarbon (hexane, hexanaphthene, kerosene, light oil etc.), ester (ethyl acetate, butylacetate etc.), nitrile (acetonitrile, isopropyl cyanide etc.), ether (Di Iso Propyl Ether, 1,4-diox etc.), acid amides (N, dinethylformamide, N,N-dimethylacetamide), halohydrocarbon (methylene dichloride, trichloroethane, tetracol phenixin etc.), methyl-sulphoxide and vegetables oil (soybean oil, the cotton seed wet goods).
Enumerated carrier gas at this, for example, fluorocarbon, butagas, liquefied petroleum gas (LPG) (LPG), dme and carbonic acid gas.
Enumerated tensio-active agent at this, for example, alkyl-sulphate, alkylsulfonate, alkylaryl sulfonate, alkyl aryl ether and their polyoxyethylene thing, polyglycol ether, polyol ester and sugar alcohol derivant.
Enumerated other pharmaceutical adjunct at this, for example, fixing agent, dispersion agent and stablizer etc., concrete as casein, gelatin, polysaccharide (starch powder, gum arabic, derivatived cellulose, Lalgine etc.), lignin derivative, wilkinite, sugar, synthesizing water-solubility polymer (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid etc.), PAP (acid phosphatase isopropyl ester), BHT (2,6 di tert butyl 4 methyl phenol), BHA (mixture of the 2-tertiary butyl-4-methoxyphenol and the 3-tertiary butyl-4-methoxyphenol), vegetables oil, mineral oil, lipid acid and fatty ester.
Enumerated poison bait matrix at this, for example, bait composition such as farm crop powder, vegetables oil, sugar, Microcrystalline Cellulose etc.In case of necessity, add antioxidant such as butylated hydroxytoluene, nordihydroguaiaretic acid etc. to poison bait, sanitas such as dehydro-acetic acid etc. prevent material that children and pet accident are eaten such as red chilly powder etc., attract the perfume compound of insect such as cheese perfume compound, onion perfume compound, peanut wet goods.
Pests controlling composition of the present invention directly is applied to the habitat (nest, plant materials, soil etc.) of insect or insect.When control parasitizes insect on the cultivated plant, for example, pests controlling composition of the present invention is sprayed on the ground segment of cultivated plant, pests controlling composition of the present invention is irrigated near the undesirable root etc.
When pests controlling composition of the present invention was used for preventing and treating the insect of agricultural and field of forestry, usage quantity was generally 0.1-10,000g The compounds of this invention/1000m 2When pests controlling composition of the present invention is an emulsion, when can flow pulvis, wettable powder, micro-capsule etc., being diluted with water to The compounds of this invention concentration usually is 10-10, uses behind the 000ppm.When pests controlling composition of the present invention is oily solution, granule, pulvis etc., also so use usually.
When pests controlling composition of the present invention was used for preventing and treating the insect in indoor field, if handle the plane, the usage quantity of The compounds of this invention was generally 0.001-100mg/m 2Use the zone, if handle the space, the usage quantity of The compounds of this invention is generally 0.001-10mg/m 3Use the zone.In use, when formulations such as pests controlling composition of the present invention is an emulsion, can flow pulvis, wettable powder, micro-capsule, the concentration that is diluted with water to The compounds of this invention usually is 0.01-100, uses behind the 000ppm.When pests controlling composition of the present invention is oily solution, aerosol, smoke substance, poison bait etc., also so use usually.
Pests controlling composition of the present invention can be used to handle the stem of plant such as crop and leaf etc. with pest control, also can be used at the plantation rice shoot handling implantation hole and undesirable root with the pre-treatment seedbed in plantation.In addition, for control survives in insect in the cultivating soil, also can handle soil with pests controlling composition of the present invention.Also the resin formulation of making sheet or wire etc. can be wrapped on the crop, be dispersed in around the crop and/or place undesirable root soil surface etc.
Pests controlling composition of the present invention also can share with other sterilant, nematicide, miticide, sterilant, weedicide, plant growth regualting composition, synergistic agent, fertilizer, soil improvement agent, animal-feed etc.
Described this sterilant, miticide and nematocides for example are:
Organo phosphorous compounds is fenitrothion 95, Tiguvon, pyridaphenthione, diazinon, Chlorpyrifos 94, chlorpyrifos_methyl, Ortho 12420, methidathion, thiodemeton, SD-1750 (DDVP), second Toyodan, Profenofos, cynock, dioxabenzofos, Rogor, Tsidial, Malathion, Trichlorphon, R-1582, monocrotophos, Carbicron, Nialate and lythidathion etc. for example; Carbamate compounds such as BPMC, benfuracarb, Propoxur, carbosulfan, carbaryl, methomyl, ethiofencarb, aldicarb, careless amine acyl, fenothiocarb, the two prestige of sulphur and alanycarb etc.; Pyrethroid compound such as ether chrysanthemum ester, kill chrysanthemum ester, esfenvalerate, Fenvalerate, Cypermethrin, α-Cypermethrin, z-Cypermethrin, permethrin, cyhalothrin, λ-cyhalothrin, cyfloxylate, β-cyfloxylate, Deltamethrin, cycloprothrin, τ-fluorine amine fenvalerate, fluoro-Cyano chrysanthemate, bifenthrin, acrinathrin, tralomethrin, salifluofen, halfenprox etc.; Neonicotine sample compound is thiophene worm piperazine, MTI-446, acetamiprid, clothianadin etc. for example; Benzoyl phenyl carbamide compound is fluorine pyridine urea, fluorobenzene urea, flufenoxuron, Acarus tritici urea etc. for example; The phenyl hydrazide compound is worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides etc. for example; Thiazine derivative is Buprofezin etc. for example; The nelicetoxin derivative is cartap, thiocyclarn, bensultap etc. for example; The hydrochloric ether compound is 5a,6,9,9a-hexahydro-6,9-methano-2,4, γ-BHC and 1 for example, two (the chloro-phenyl-)-trichloro-ethyl alcohol of 1-etc.; Carboxamidine derivatives is U-36059 and chlordimeform etc. for example; It is grand etc. that thiourea derivative for example kills mite sulphur; Phenyl pyrazole compounds for example second sulphur worm internal organs, second phthalein worm is cured etc.; Chlorfenapyr pyrrole ketone, pleocidin, indenes worm prestige, pyridalyl, the pyrrole propyl ether, fenoxycarb, difenolan, cyromazine, bromopropylate, tetradifon, chinomethionate, alkynes mite spy, fenbutatin oxide, hexythiazox, second mite azoles, four mite piperazines, pyridaben, azoles mite ester, tebufenpyrad, pyrimidifen, fenazaquin, the mite quinone goes out, Bifenazate, Fluacrypyrim, spiral shell mite ester, season ketone first mite ester, the close spit of fland of going out, Avrmectin, the phenylformic acid Affirm (Merck Co.), nimbin (azadilactin), compound polynactin [polynactin for example, the diformazan polynactin, one first polynactin] etc.
By further sets forth in detail the present invention such as following example of formulations and test implementation example, but the present invention is not limited to these embodiment.
Except as otherwise noted, in production example with in reference to production example, for 1H-NMR, the data of mensuration as interior mark, are shown as the form of chemical shift (δ [ppm] value) with the tetramethyl-silicomethane in the deuteriochloroform solvent.
[work embodiment]
Production example 1
0.3g 4-(2-butyne oxygen base)-6-chloro-5-fluorine pyrimidine is dissolved in the 3ml ethanol, adds 0.45g2-methyl piperidine (2-methylpyperidine), the mixture reflux conditions stirred 5 hours down.Reaction mixture is cooled near room temperature, concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.28g 4-(2-butyne oxygen base)-5-fluoro-6-(pipecoline subbase) pyrimidine (being called compound (1) hereinafter).
1H-NMR：1.25(d，3H)，1.58-1.79(m，6H)，1.88(t，3H)，3.14-3.18(m，1H)，4.21-4.24(m，1H)，4.65-4.78(m，1H)，4.97(q，2H)，8.04(s，1H)
Production example 2
0.3g 4-(2-butyne oxygen base)-6 chloro-5-fluorine pyrimidines are dissolved in the 3ml ethanol, to wherein adding the 0.38g piperidines, the mixture reflux conditions stirred 7 hours down.Reaction mixture is cooled near room temperature, concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.37g 4-(2-butyne oxygen base)-5-fluoro-6-piperidinopy rimidine (being called compound (2) hereinafter).
1H-NMR：1.60-1.72(m，6H)，1.87(t，3H)，3.63-3.69(m，4H)，4.97(q，2H)，8.04(s，1H)
Production example 3
0.3g 4-(2-butyne oxygen base)-6-chloro-5-fluorine pyrimidine is dissolved in the 3ml ethanol, adds the 0.45g3-methyl piperidine, the mixture reflux conditions stirred 10 hours down.Reaction mixture is cooled near room temperature, concentrates.Add saturated aqueous ammonium chloride in resistates, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.37g 4-(2-butyne oxygen base)-5-fluoro-6-(3-methyl piperidine subbase) pyrimidine (being called compound (3) hereinafter).
Figure A20048001247300331
1H-NMR:0.92 (d, 3H), 1.17-1.23 (m, 1H), 1.52-1.77 (m, 3H), 1.81-1.91 (m, 4H comprises the triplet at 1.87 places), and 2.60-2.64 (m, 1H), 2.92-3.01 (m, 1H), 4.26-4.3s (m, 2H), 4.97 (q, 2H), 8.04 (s, 1H)
Production example 4
0.3g 4-(2-butyne oxygen base)-6-chloro-5-fluorine pyrimidine is dissolved in the 3ml ethanol, adds 0.51g3,5-lupetidine (suitable/anti-=about 3/1), and the mixture reflux conditions stirred 8 hours down.Reaction mixture is cooled near room temperature, concentrates.Add saturated aqueous ammonium chloride in resistates, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.40g 4-(2-butyne oxygen base)-5-fluoro-6-(3,5-lupetidine subbase) pyrimidines (being called compound (4) hereinafter).Because two methyl are arranged on piperidine ring, compound (4) has suitable/anti-diastereomer.The ratio of suitable/anti-diastereomer is about 3.3/1.
Figure A20048001247300332
1H-NMR:0.80 (dd, 1H), 0.91 (d, 6H), 1.60-1.72 (m, 2H), 1.81-1.89 (m, 4H comprise the triplet at 1.87 places), 2.40 (dd, 2H), 4.39 (dd, 2H), 4.97 (q, 2H), 8.03 (s, 1H); 0.94 (s), 1.49 (t), 1.94-2.03 (m), 3.31 (dd), 3.75 (dd), 8.01 (s)
Production example 5
0.3g 4-(2-butyne oxygen base)-6-chloro-5-fluorine pyrimidine is dissolved in the 3ml ethanol, adds the 0.45g hexamethylene imine, the mixture reflux conditions stirred 10 hours down.Reaction mixture is cooled near room temperature, concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.29g 1-{6-(2-butyne oxygen base)-5-fluoro-4-pyrimidyl } six hydrogen-1H-azepan (being called compound (5) hereinafter).
Figure A20048001247300341
1H-NMR：1.56-1.60(m，4H)，1.77-1.81(m，4H)，1.87(t，3H)，3.74-3.77(m，4H)，4.97(q，2H)，8.01(s，1H)
Production example 6
0.2g 4-(2-butyne oxygen base)-6-chloro-5-fluorine pyrimidine and 0.30g 2, the 5-dimethyl pyrrolidine is mixed, places 18 hours under the room temperature.Add saturated aqueous ammonium chloride in reaction mixture, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.25g 4-(2-butyne oxygen base)-5-fluoro-6-(2,5-dimethyl-1-pyrrolidyl) pyrimidines (being called compound (6) hereinafter).
1H-NMR：1.33(d，6H)，1.70-1.76(m，2H)，1.87(t，3H)，2.01-2.07(m，2H)，4.26-4.34(m，2H)，4.97(q，2H)，8.03(s，1H)
Production example 7
0.3g 4-(2-butyne oxygen base)-6-chloropyrimide is dissolved in 3ml ethanol, adds 0.56g 3,5-lupetidine (suitable/anti-=about 3/1), and the mixture reflux conditions stirred 10 hours down.Reaction mixture is cooled near room temperature, concentrates.Add saturated aqueous ammonium chloride in resistates, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.44g 4-(2-butyne oxygen base)-6-(3,5-lupetidine subbase) pyrimidines (being called compound (7) hereinafter).Because two methyl are arranged on piperidine ring, compound (7) has suitable/anti-diastereomer.The ratio of suitable/anti-diastereomer is about 3.1/1.
Figure A20048001247300351
1H-NMR:0.81 (dd, 1H), 0.92 (d, 6H), 1.55-1.68 (m, 2H), 1.80-1.89 (m, 4H comprise the triplet at 1.86 places), 2.31 (dd, 2H), 4.23 (dd, 2H), 4.91 (q, 2H), 5.87 (s, 1H), 8.29 (s, 1H); 1.49 (t), 1.89-1.99 (m), 3.18 (dd), 3.64 (dd), 5.85 (s), 8.27 (s)
Production example 8
0.3g 4-(2-butyne oxygen base)-5, the 6-dichloro pyrimidine is dissolved in 3ml ethanol, adds 0.47g 3,5-lupetidine (suitable/anti-=about 3/1), and the mixture reflux conditions stirred 8 hours down.Reaction mixture is cooled near room temperature, concentrates.Add saturated aqueous ammonium chloride in resistates, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.36g 4-(2-butyne oxygen base)-5-chloro-6-(3,5-lupetidine subbase) pyrimidines (being called compound (8) hereinafter).Because two methyl are arranged on piperidine ring, compound (8) has suitable/anti-diastereomer.The ratio of suitable/anti-diastereomer is about 3.6/1.
1H-NMR:0.77 (dd, 1H), 0.91 (d, 6H), 1.70-1.91 (m, 6H comprise the triplet at 1.86 places), 2.38 (dd, 2H), 4.24 (dd, 2H), 4.99 (q, 2H), 8.22 (s, 1H); 0.97 (d), 1.45-1.48 (m), 2.05-2.09 (m), 3.28 (dd), 3.59 (dd)
Production example 9
0.3g 4-(2-butyne oxygen base)-6-chloro-5-methylpyrimidine is dissolved in 3ml ethanol, adds 0.47g3,5-lupetidine (suitable/anti-=about 3/1), and the mixture reflux conditions stirred 16 hours down.Reaction mixture is cooled near room temperature, concentrates.Add saturated aqueous ammonium chloride in resistates, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.33g 4-(2-butyne oxygen base)-5-methyl-6-(3,5-lupetidine subbase) pyrimidines (being called compound (9) hereinafter).Because two methyl are arranged on piperidine ring, compound (9) has suitable/anti-diastereomer.The ratio of suitable/anti-diastereomer is about 3.8/1.
1H-NMR:0.75 (dd, 1H), 0.91 (d, 6H), 1.71-1.89 (m, 6H comprise the triplet at 1.87 places), 2.06 (s, 3H), 2.34 (dd, 2H), 3.67 (dd, 2H), 4.95 (q, 2H), 8.33 (s, 1H); 1.01 (d), 1.43-1.47 (m), 2.09 (s), 2.94 (dd), 3.29 (dd)
Production example 10
0.2g 4-chloro-5-fluoro-6-(valerylene oxygen base) pyrimidine and 0.29g 3-methyl piperidine are mixed, place 3 hours under the room temperature.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.23g 5-fluoro-4-(3-methyl piperidine subbase)-6-(valerylene oxygen base) pyrimidine (being called compound (10) hereinafter).
1H-NMR:0.92 (d, 3H), 1.12-1.23 (m, 4H comprise the triplet at 1.14 places), 1.52-1.77 (m, 3H), 1.82-1.89 (m, 1H), 2.24 (qt, 2H), 2.62 (dd, 1H), 2.95 (dd, 1H), 4.26-4.34 (m, 2H), 4.99 (t, 2H), 8.03 (s, 1H)
Production example 11
0.2g 4-chloro-5-fluoro-6-(valerylene oxygen base) pyrimidine and 0.32g 3,5-lupetidine (suitable/anti-=about 3/1) is mixed, places 3 hours under the room temperature.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.23g 4-(3,5-lupetidine subbase)-5-fluoro-6-(valerylene oxygen base) pyrimidine (hereinafter, being called compound (11)).Because two methyl are arranged on piperidine ring, compound (11) has suitable/anti-diastereomer.The ratio of suitable/anti-diastereomer is about 3.8/1.
1H-NMR：0.80(dd，1H)，0.91(d，6H)，1.14(t，3H)，1.63-1.75(m，2H)，1.80-1.88(m，1H)，2.24(qt，2H)，2.40(dd，2H)，4.39(dd，2H)，4.99(t，2H)，8.03(s，1H)；0.94(d)，1.46-1.49(m)，1.93-2.02(m)，3.31(dd)，3.75(dd)，8.01(s)
Production example 12
0.2g 4-chloro-5-fluoro-6-(valerylene oxygen base) pyrimidine and 0.24g piperidines are mixed, place 3 hours under the room temperature.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.24g 5-fluoro-4-piperidino-(1-position only)-6-(valerylene oxygen base) pyrimidine (being called compound (12) hereinafter).
Figure A20048001247300372
1H-NMR：1.14(t，3H)，1.60-1.71(m，6H)，2.24(qt，2H)，3.67-3.71(m，4H)，4.99(t，2H)，8.03(s，1H)
Production example 13
0.2g 4-chloro-5-fluoro-6-(valerylene oxygen base) pyrimidine and 0.2g 2, the 5-dimethyl pyrrolidine is mixed, places 13 hours under the room temperature.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.12g 4-(2,5-dimethyl-1-pyrrolidyl)-5-fluoro-6-(valerylene oxygen base) pyrimidine (being called compound (13) hereinafter).
Figure A20048001247300381
1H-NMR：1.15(t，3H)，1.33(d，6H)，1.69-1.78(m，2H)，2.00-2.09(m，2H)，2.24(qt，2H)，4.24-4.33(m，2H)，4.99(t，2H)，8.03(s，1H)
Production example 14
0.2g 4-chloro-5-fluoro-6-(valerylene oxygen base) pyrimidine and 0.28g hexamethylene imine are mixed, place 3 hours under the room temperature.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.26g 1-{5-fluoro-6-(valerylene oxygen base)-4-pyrimidyl) six hydrogen-1H-azepan (being called compound (14) hereinafter).
Figure A20048001247300382
1H-NMR：1.15(t，3H)，1.52-1.61(m，4H)，1.72-1.79(m，4H)，2.24(qt，2H)，3.65-3.74(m，4H)，4.99(t，2H)，8.01(s，1H)
Production example 15
0.07g sodium hydride (60% oil suspension) is suspended in the 2ml tetrahydrofuran (THF).To the 0.5ml tetrahydrofuran solution that wherein drips 0.13g valerylene-1-alcohol, mixture stirred 10 minutes under 0 ℃.In mixture, drip the tetrahydrofuran solution of 0.3g 4-chloro-6-(3, the 5-lupetidine subbase) pyrimidine of 0.5ml reference example 6 gained, stirred 6 hours under the room temperature.Add saturated aqueous ammonium chloride in reaction mixture, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.15g 4-(3,5-lupetidine subbase)-6-(valerylene oxygen base) pyrimidine (being called compound (15) hereinafter).Because two methyl are arranged on piperidine ring, compound (15) has suitable/anti-diastereomer.The ratio of suitable/anti-diastereomer is about 8.2/1.
1H-NMR：0.81(dd，1H)，0.92(d，6H)，1.15(t，3H)，1.55-1.72(m，2H)，1.80-1.87(m，1H)，2.20-2.36(m，4H)，4.23-4.26(m，2H)，4.93(t，2H)，5.88(s，1H)，8.29(s，1H)；1.89-2.00(m)，3.18(dd)，3.64(dd)，5.86(s)，8.27(s)
Production example 16
183mg 4-chloro-6-(2-butyne oxygen base) pyrimidine is dissolved in 2ml N, dinethylformamide, and to wherein adding 166mg salt of wormwood and 85mg piperidines, 80 ℃ of following mixtures stirred 5 hours.Reaction mixture adds ethyl acetate near room temperature, and mixture washs 3 times with saturated sodium-chloride water solution.The organic phase anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 178mg 4-(2-butyne oxygen base)-6-piperidinopy rimidine (being called compound (16) hereinafter).
Figure A20048001247300392
1H-NMR：1.5-1.8(m，6H)，1.87(t，3H)，3.55(t，4H)，4.91(q，2H)，5.86(s，1H)，8.30(s，1H)
Production example 17
183mg 4-chloro-6-(2-butyne oxygen base) pyrimidine is dissolved in 2ml N, dinethylformamide, and to wherein adding 166mg salt of wormwood and 71mg tetramethyleneimine, 55-60 ℃ of following mixture stirred 4 hours.Reaction mixture adds ethyl acetate near room temperature, and mixture washs 3 times with saturated sodium-chloride water solution.The organic phase anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 170mg 4-(2-butyne oxygen base)-6-(1-pyrrolidyl) pyrimidine (being called compound (17) hereinafter).
1H-NMR：1.87(t，3H)，2.00(brs，4H)，3.45(brs，4H)，4.92(q，2H)，5.65(s，1H)，8.30(s，1H)
Production example 18
183mg 4-chloro-6-(2-butyne oxygen base) pyrimidine is dissolved in 2ml N, dinethylformamide, and to wherein adding 166mg salt of wormwood and 99mg 4-methyl piperidine, 80 ℃ of following mixtures stirred 4 hours.Reaction mixture adds ethyl acetate near room temperature, and mixture washs 3 times with saturated sodium-chloride water solution.The organic phase anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 206mg 4-(2-butyne oxygen base)-6-(4-methyl piperidine subbase) pyrimidine (being called compound (18) hereinafter).
Figure A20048001247300402
1H-NMR：0.96(d，3H)，1.0-1.3(m，2H)，1.5-1.8(m，3H)，1.87(t，3H)，2.85(dt，2H)，4.2-4.35(m，2H)，4.91(q，2H)，5.87(s，1H)，8.30(s，1H)
Production example 19
183mg 4-chloro-6-(2-butyne oxygen base) pyrimidine is dissolved in 2m1N, dinethylformamide, and to wherein adding 166mg salt of wormwood and 99mg 3-methyl piperidine, 80 ℃ of following mixtures stirred 4 hours.Reaction mixture adds ethyl acetate near room temperature, and mixture washs 3 times with saturated sodium-chloride water solution.The organic phase anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 181mg 4-(2-butyne oxygen base)-6-(3-methyl piperidine subbase) pyrimidine (being called compound (19) hereinafter).
Figure A20048001247300411
1H-NMR：0.93(d，3H)，1.05-1.3(m，1H)，1.4-1.85(m，4H)，1.87(t，3H)，2.45-2.6(m，1H)，2.85(dt，1H)，4.1-4.25(m，2H)，4.91(q，2H)，5.87(s，1H)，8.30(s，1H)
Production example 20
183mg 4-chloro-6-(2-butyne oxygen base) pyrimidine is dissolved in 2ml N, dinethylformamide, and to wherein adding 166mg salt of wormwood and 99mg pipecoline, mixture stirred 4 hours down at 80 ℃, stirred 3 hours down at 120 ℃.Reaction mixture adds ethyl acetate near room temperature, and mixture washs 3 times with saturated sodium-chloride water solution.The organic phase anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 66mg 4-(2-butyne oxygen base)-6-(pipecoline subbase) pyrimidine (being called compound (20) hereinafter).
Figure A20048001247300412
1H-NMR：1.16(d，3H)，1.4-1.6(m，1H)，1.6-1.8(m，5H)，1.87(t，3H)，2.91(dt，1H)，4.1-4.2(m，1H)，4.5-4.6(m，1H)，4.91(q，2H)，5.84(s，1H)，8.30(s，1H)
Production example 21
183mg 4-chloro-6-(2-butyne oxygen base) pyrimidine is dissolved in 2ml N, dinethylformamide, and to wherein adding 166mg salt of wormwood and 85mg 2-crassitude, 60 ℃ of following mixtures stirred 7 hours.Reaction mixture adds ethyl acetate near room temperature, and mixture washs 3 times with saturated sodium-chloride water solution.The organic phase anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 207mg 4-(2-butyne oxygen base)-6-(2-methyl-tetramethyleneimine-1-yl) pyrimidine (being called compound (21) hereinafter).
1H-NMR：1.21(d，3H)，1.6-1.8(m，1H)，1.88(t，3H?)，1.9-2.1(m，3H)，3.2-3.4(m，1H)，3.4-3.6(m，1H)，4.0-4.2(m，1H)，4.92(q，2H)，5.66(s，1H)，8.31(s，1H)
Production example 22
0.3g 4-chloro-6-(2-butyne oxygen base) pyrimidine mixes with 0.56g 2-ethyl piperidine, places 18 hours down for 80 ℃.Reaction mixture is carried out the silica gel column chromatography chromatography near room temperature, obtains 0.14g 4-(2-butyne oxygen base)-6-(2-ethyl piperidine subbase) pyrimidine (being called compound (22) hereinafter).
Figure A20048001247300422
1H-NMR：0.86(t，3H)，1.41-1.78(m，8H)，1.87(t，3H)，2.89(td，2H)，4.14-3.38(m，2H)，4.91(q，2H)，5.83(s，1H)，8.28(s，1H)
Production example 23
0.3g 4-chloro-6-(2-butyne oxygen base) pyrimidine is dissolved in 3ml N, dinethylformamide, and 0.57g salt of wormwood and 0.25g hydrochloric acid are suitable-3 to wherein adding, the 5-lupetidine, 70 ℃ of following mixtures stirred 40 minutes.Reaction mixture adds saturated aqueous ammonium chloride near room temperature, and mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed 3 times with saturated sodium-chloride water solution.The organic phase anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.41g 4-(2-butyne oxygen base)-6-(suitable-3,5-lupetidine subbase) pyrimidine (being called compound (23) hereinafter).
Figure A20048001247300431
1H-NMR:0.80 (dd, 1H), 0.92 (d, 6H), 1.54-1.67 (m, 2H), 1.79-1.88 (m, 4H comprise the triplet at 1.86 places), 2.31 (dd, 2H), 4.25 (dd, 2H), 4.91 (q, 2H), 5.87 (s, 1H), 8.30 (s, 1H)
Production example 24
0.3g 4-chloro-6-(2-butyne oxygen base) pyrimidine mixes with 0.25g 3-trifluoromethyl piperidines, places 10 hours under the room temperature.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.30g 4-(2-butyne oxygen base)-6-(3-trifluoromethyl piperidino-(1-position only)) pyrimidine (being called compound (24) hereinafter).
Figure A20048001247300432
1H-NMR:1.36-1.60 (m, 2H), 1.72-1.83 (m, 4H comprise the triplet at 1.87 places), 1.95-2.14 (m, 1H), 2.19-2.24 (m, 1H), 2.75-2.84 (m, 2H), 4.13 (brd, 1H), 4.53 (brd, 1H), 4.84 (q, 2H), 5.82 (s, 1H), 8.24 (s, 1H)
Production example 25
0.2g 4-chloro-6-(valerylene oxygen base) pyrimidine mixes with 0.23g 3-trifluoromethyl piperidines, places 10 hours under the room temperature.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.15g 6-(valerylene oxygen base)-4-(3-trifluoromethyl piperidino-(1-position only)) pyrimidine (being called compound (25) hereinafter).
1H-NMR：1.15(t，3H)，1.45-1.68(m，2H)，1.79-1.88(m，1H)，2.04-2.13(m，1H)，2.25(qt，3H)，2.80-2.93(m，2H)，4.22(brd，1H)，4.61(brd，1H)，4.95(q，2H)，5.92(s，1H)，8.33(s，1H)
Production example 26
0.2g 4-(2-butyne oxygen base)-5-fluoro-6-chloropyrimide is dissolved in 2ml N, dinethylformamide, and to wherein adding 0.28g salt of wormwood and 0.15g 3-trifluoromethyl piperidines, 70 ℃ of following mixtures stirred 5 hours.Reaction mixture adds ethyl acetate near room temperature, and mixture washs 3 times with saturated sodium-chloride water solution.The organic phase anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.28g 4-(2-butyne oxygen base)-5-fluoro-6-(3-trimethyl-piperidine subbase) pyrimidine (being called compound (26) hereinafter).
Figure A20048001247300441
1H-NMR:1.54-1.68 (m, 2H), 1.81-1.90 (m, 4H comprise the triplet at 1.87 places), 2.05-2.14 (m, 1H), 2.30-2.44 (m, 1H), 2.92-3.02 (m, 2H), 4.38 (brd, 1H), 4.65 (q, 1H), 4.99 (q, 2H), 8.08 (s, 1H)
Production example 27
0.37g 4-(2-butyne oxygen base)-6-chloropyrimide is dissolved in 4ml N, dinethylformamide, and to wherein adding 0.56g salt of wormwood and 0.2g 3, the 3-dimethyl pyrrolidine, 80 ℃ of following mixtures stirred 6 hours.Reaction mixture adds ethyl acetate near room temperature, and mixture washs 3 times with saturated sodium-chloride water solution.The organic phase anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.11g 4-(2-butyne oxygen base)-6-(3,3-dimethyl pyrrolidine-1-yl) pyrimidines (being called compound (27) hereinafter).
Figure A20048001247300442
1H-NMR：1.13(s，6H)，1.75-1.84(m，2H)，1.87(t，3H)，2.94-3.75(br，4H)，4.092(q，2H，)，5.62(s，1H)，8.31(s，1H)
Production example 28
0.36g 4-(2-butyne oxygen base)-6-chloro-5-fluorine pyrimidine is dissolved in 4ml N, dinethylformamide, and to wherein adding 0.62g salt of wormwood and 0.25g 3, the 3-dimethyl pyrrolidine, 80 ℃ of following mixtures stirred 6 hours.Reaction mixture adds ethyl acetate near room temperature, and mixture washs 3 times with saturated sodium-chloride water solution.The organic phase anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.15g 4-(2-butyne oxygen base)-5-fluoro-6-(3,3-dimethyl pyrrolidine-1-yl) pyrimidines (being called compound (28) hereinafter).
Figure A20048001247300451
1H-NMR：1.13(s，6H)，1.73(t，2H)，1.87(t，3H)，3.42(d，2H)，3.76(td，2H)，4.97(q，2H，)，8.02(s，1H)
Production example 29
0.10g sodium hydride (60% oil suspension) is suspended in the 3ml tetrahydrofuran (THF).To the 1ml tetrahydrofuran solution that wherein drips 0.16g 2-butyne-1-alcohol, mixture stirred 10 minutes.Drip the 1ml tetrahydrofuran solution of 0.31g 4-chloro-6-(suitable-3,5-lupetidine subbase)-5-fluorine pyrimidine in this mixture, 60 ℃ were stirred 6 hours down.Add saturated aqueous ammonium chloride in reaction mixture, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.32g 4-(2-butyne oxygen base)-5-fluoro-6-(suitable-3,5-lupetidine subbase) pyrimidine (being called compound (29) hereinafter).
Figure A20048001247300452
1H-NMR:0.80 (dd, 1H), 0.91 (d, 6H), 1.63-1.76 (m, 2H), 1.81-1.88 (m, 4H comprise the triplet at 1.87 places), 2.40 (dd, 2H), 4.39 (dd, 2H), 4.97 (q, 2H), 8.04 (s, 1H)
Production example 30
0.16g sodium hydride (60% oil suspension) is suspended in the 4ml tetrahydrofuran (THF).To the 1ml tetrahydrofuran solution that wherein drips 0.27g 2-butyne-1-alcohol, mixture stirred 10 minutes under the room temperature.Drip the 1ml tetrahydrofuran solution of 0.64g 4-chloro-6-(3,5-diethyl piperidino-(1-position only)) pyrimidine in this mixture, wherein the ratio of suitable on the piperidine ring/anti-diastereomer is 1: 1, and 60 ℃ were stirred 5 hours down.Add saturated aqueous ammonium chloride in reaction mixture, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.41g 4-(2-butyne oxygen base)-6-(3,5-diethyl piperidino-(1-position only)) pyrimidines (being called compound (30) hereinafter).Because two ethyls are arranged on piperidine ring, compound (30) has suitable/anti-diastereomer.The ratio of suitable/anti-diastereomer is about 1/1.
1H-NMR：0.73(dd，0.5H)，0.88-0.95(m，6H)，1.07(t，0.5H)，1.20-1.42(m，4H)，1.52-1.64(m，2H)，1.80-1.99(m，4H)，2.34(dd，1H)，3.30(dd，1H)，3.62(dd，1h)，4.28-4.37(m，1H)，4.90-4.93(m，2H)，5.85(s，0.5H)，5.87(s，0.5H)，8.27(s，0.5H)，8.30(s，0.5)
Production example 31
0.20g 4-(2-butyne oxygen base)-6-chloropyrimide, 0.45g salt of wormwood and 0.20g hydrochloric acid 3, the 3-lupetidine joins in the 2ml acetonitrile (acetnitrile), stirs the mixture 2 hours under 80 ℃.Reaction mixture is extremely near room temperature, and to wherein adding saturated aqueous ammonium chloride, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.27g 4-(2-butyne oxygen base)-6-(3,3-lupetidine subbase) pyrimidines (being called compound (31) hereinafter).
Figure A20048001247300471
Production example 32
0.12g sodium hydride (60% oil suspension) is suspended in the 2ml tetrahydrofuran (THF).To wherein adding 0.18g hydrochloric acid 3,3-lupetidine and 0.20g 4-(2-butyne oxygen base)-6-chloro-5-fluorine pyrimidine stirred the mixture 1 hour under 60 ℃.The question response mixture is cooled near after the room temperature, and to wherein adding saturated aqueous ammonium chloride, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.05g 4-(2-butyne oxygen base)-6-(3,3-lupetidine subbase)-5-fluorine pyrimidine (being called compound (32) hereinafter).
Figure A20048001247300472
1H-NMR：0.93(s，6H)，1.43-1.48(m，2H)，1.61-1.72(m，2H)，1.87(t，3H)，3.39(s，2H)，3.62-3.67(m，2H)，4.97(q，2H)，8.02(s，1H)
Production example 33
0.05g sodium hydride (60% oil suspension) is suspended in the 2ml tetrahydrofuran (THF).To the 0.5ml tetrahydrofuran solution that wherein drips 0.08g 2-butyne-1-alcohol, mixture stirred 10 minutes under the room temperature.Drip the 0.5ml tetrahydrofuran solution of 0.22g 4-chloro-6-(2-ethyl piperidine subbase) pyrimidine under the room temperature in mixture, 60 ℃ were stirred 6 hours down.Reaction mixture to be cooled is extremely near after the room temperature, and to wherein adding saturated aqueous ammonium chloride, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.23g 4-(2-butyne oxygen base)-6-(2-ethyl piperidine subbase)-5-fluorine pyrimidine (being called compound (33) hereinafter).
1H-NMR:0.87 (t, 3H), 1.48-1.72 (m, 7H), 1.76-1.89 (m, 4H comprise the triplet at 1.87 places), 3.05 (td, 1H), 4.27-4.33 (m, 1H), 4.45-4.53 (m, 1H), 4.97 (q, 2H), 8.03 (s, 1H)
Production example 34
0.08g sodium hydride (60% oil suspension) is suspended in the 3ml tetrahydrofuran (THF).To the 0.5ml tetrahydrofuran solution that wherein drips 0.15g 2-butyne-1-alcohol, mixture stirred 10 minutes under the room temperature.In mixture, drip 0.33g 1-(6-chloropyrimide-4-yl)-2 under the room temperature, the 0.5ml tetrahydrofuran solution of 5-dimethyl six hydrogen-1H-azepan, 60 ℃ were stirred 4 hours down.Reaction mixture to be cooled is extremely near after the room temperature, and to wherein adding saturated aqueous ammonium chloride, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.17g 1-(6-(2-butyne oxygen base) pyrimidine-4-yl)-2,5-dimethyl six hydrogen-1H-azepan (being called compound (34) hereinafter).
Figure A20048001247300482
GC-MS：273(M+)
Production example 35
0.07g sodium hydride (60% oil suspension) is suspended in the 3ml tetrahydrofuran (THF).To the 0.5ml tetrahydrofuran solution that wherein drips 0.12g 2-butyne-1-alcohol, mixture stirred 10 minutes under the room temperature.In mixture, drip 0.34g 1-(6-chloro-5-fluorine pyrimidine-4-yl)-2 under the room temperature, the 0.5ml tetrahydrofuran solution of 5-dimethyl-six hydrogen-1H-azepan, 60 ℃ were stirred 8 hours down.Reaction mixture to be cooled is extremely near after the room temperature, and to wherein adding saturated aqueous ammonium chloride, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.35g 1-(6-(2-butyne oxygen base)-5-fluorine pyrimidine-4-yl)-2,5-dimethyl-six hydrogen-1H-azepan (being called compound (35) hereinafter).
Figure A20048001247300491
1H-NMR:0.89 (d, 3H), 1.04-1.16 (m, 4H comprise the bimodal of 1.15 places), 1.25-1.70 (m, 4H), 1.78-1.89 (m, 4H comprise the triplet at 1.87 places), 2.02 (ddd, 1H), 3.01 (dd, 1H), 3.95 (brd, 1H), 4.47-4.58 (br, 1H), 4.97 (q, 2H), 8.03 (s, 1H)
Production example 36
0.20g 4-(2-butyne oxygen base)-6-chloro-5-fluorine pyrimidine, 0.41g salt of wormwood and 0.20g hydrochloric acid 3,4-dimethyl pyrrolidine (along anti-non-enantiomer mixture) joins in the 3ml acetonitrile, stirs the mixture 7 hours under 80 ℃.Reaction mixture is extremely near room temperature, and to wherein adding saturated aqueous ammonium chloride, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.20g 4-(2-butyne oxygen base)-6-(3,4-dimethyl pyrrolidine-1-yl)-5-fluorine pyrimidine (being called compound (36) hereinafter).
1H-NMR:0.99 (d, 0.6H), 1.08 (d, 2.4H), (1.74-1.88 m, 4.6H comprise the triplet at 1.87 places), and 2.29-2.35 (m, 0.4H), 3.15-3.24 (ml, 1.6H), 3.36-3.43 (m, 0.4H), 3.73-3.80 (m, 0.4H), 3.90-3.98 (m, 1.6H), 4.97 (q, 2H), 8.02 (s, 1H)
GC-Ms：263(M+)；263(M+)
Production example 37
0.30g 4-(2-butyne oxygen base)-6-chloropyrimide, 0.68g salt of wormwood and 0.33g hydrochloric acid 3,4-dimethyl pyrrolidine (along anti-non-enantiomer mixture) joins in the 3ml acetonitrile, stirs the mixture 4 hours under 70 ℃.Reaction mixture is extremely near room temperature, and to wherein adding saturated aqueous ammonium chloride, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.42g 4-(2-butyne oxygen base)-6-(3,4-dimethyl pyrrolidine-1-yl) pyrimidines (being called compound (37) hereinafter).
1H-NMR:0.99 (d, 1.2H), 1.09 (d, 4.8H), 1.74-1.88 (m, 4.6H comprise the triplet at 1.87 places), 2.14-2.42 (m, 0.4H), 2.80-4.06 (m, 4H), 4.92 (q, 2H), 5.61 (s, 1H), 8.29 (s, 1H) GC-MS:245 (M+); 245 (M+)
Production example 38
0.20g 4-(2-butyne oxygen base)-6-chloropyrimide, 0.45g salt of wormwood and 0.24g hydrochloric acid 3,3,5, the 5-tetramethyl piperidine joins in the 2ml acetonitrile, stirs the mixture 4 hours under 60 ℃.Reaction mixture is extremely near room temperature, and to wherein adding saturated aqueous ammonium chloride, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.23g 4-(2-butyne oxygen base)-6-(3,3,5,5-tetramethyl piperidine subbase) pyrimidines (being called compound (38) hereinafter).
1H-NMR：0.97(s，12H)，1.32(s，2H)，1.87(t，3H)，3.30(s，4H)，4.91(q，2H)，5.88(s，1H)，8.27(s，1H)
Production example 39
0.20g 4-(2-butyne oxygen base)-6-chloro-5-fluorine pyrimidine, 0.54g salt of wormwood and 0.30g hydrochloric acid 3,3,5, the 5-tetramethyl piperidine joins in the 2ml acetonitrile, stirs the mixture 4 hours under 70 ℃.Reaction mixture is extremely near room temperature, and to wherein adding saturated aqueous ammonium chloride, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.22g 4-(2-butyne oxygen base)-5-fluoro-6-(3,3,5,5-tetramethyl piperidine subbase) pyrimidines (being called compound (39) hereinafter).
Figure A20048001247300511
1H-NMR：0.99(s，12H)，1.33(s，2H)，1.87(t，3H)，3.41(s?，4H)，4.97(q，2H)，8.01(s，1H)
m.p.：85.3
Production example 40
0.07g sodium hydride (60% oil suspension) is suspended in the 3ml tetrahydrofuran (THF).To the 0.5ml tetrahydrofuran solution that wherein drips 0.11g 2-butyne-1-alcohol, mixture stirred 10 minutes under the room temperature.In mixture, drip 0.30g 1-(6-chloropyrimide-4-yl)-suitable-2 under the room temperature, the 0.5ml tetrahydrofuran solution of 6-dimethyl-six hydrogen-1H-azepan, 60 ℃ were stirred 8 hours down.Reaction mixture to be cooled pours into reaction mixture in the saturated aqueous ammonium chloride near after the room temperature, and mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.25g 1-(6-(2-butyne oxygen base) pyrimidine-4-yl)-suitable-2,6-dimethyl-six hydrogen-1H-azepan (being called compound (40) hereinafter).
Figure A20048001247300521
GC-MS：273(M+)
Production example 41
0.10g sodium hydride (60% oil suspension) is suspended in the 3ml tetrahydrofuran (THF).To the 0.5ml tetrahydrofuran solution that wherein drips 0.15g 2-butyne-1-alcohol, mixture stirred 10 minutes under the room temperature.In mixture, drip 0.30g 1-(6-chloro-5-fluorine pyrimidine-4-yl)-suitable-2 under the room temperature, the 0.5ml tetrahydrofuran solution of 6-dimethyl-six hydrogen-1H-azepan, 70 ℃ were stirred 8 hours down.Reaction mixture to be cooled pours into reaction mixture in the saturated aqueous ammonium chloride near after the room temperature, and mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.36g 1-(6-(2-butyne oxygen base)-5-fluorine pyrimidine-4-yl)-suitable-2,6-dimethyl-six hydrogen-1H-azepan (being called compound (41) hereinafter).
Figure A20048001247300522
1H-NMR:0.90-1.01 (m, 4H comprise the bimodal of 0.92 place), 1.14 (d, 3H), 1.24-1.43 (m, 2H), 1.69-1.89 (m, 6H comprise the triplet at 1.87 places), 2.03-2.11 (m, 1H), 2.86 (td, 1H), 3.68 (dd, 1H), 4.59 (brs, 1H), 4.97 (q, 2H), 8.02 (s, 1H)
GC-MS：291(M+)
Production example 42
0.10g sodium hydride (60% oil suspension) is suspended in the 3ml tetrahydrofuran (THF).To the 0.5ml tetrahydrofuran solution that wherein drips 0.15g 2-butyne-1-alcohol, mixture stirred 10 minutes under the room temperature.In mixture, drip 0.31g 1-(6-chloro-5-fluorine pyrimidine-4-yl)-anti--2 under the room temperature, the 0.5ml tetrahydrofuran solution of 6-dimethyl-six hydrogen-1H-azepan, 60 ℃ were stirred 6 hours down.Reaction mixture to be cooled pours into reaction mixture in the saturated aqueous ammonium chloride near after the room temperature, and mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.34g 1-(6-(2-butyne oxygen base)-5-fluorine pyrimidine-4-yl)-anti--2,6-dimethyl-six hydrogen-1H-azepan (being called compound (42) hereinafter).
Figure A20048001247300531
1H-NMR：0.90(d，3H)，1.16(d，3H)，1.42-1.61(m，5H)，1.87(t，3H)，1.89-2.05(m，2H)，3.35(d，1H)，4.14(dd，1H)，4.42-4.51(m，1H)，4.97(q，2H)，8.01(s，1H)
GC-MS：291(M+)
Production example 43
0.10g sodium hydride (60% oil suspension) is suspended in the 3ml tetrahydrofuran (THF).To the 0.5ml tetrahydrofuran solution that wherein drips 0.16g 2-butyne-1-alcohol, mixture stirred 10 minutes under the room temperature.In mixture, drip 0.30g 1-(6-chloropyrimide-4-yl)-anti--2 under the room temperature, the 0.5ml tetrahydrofuran solution of 6-dimethyl-six hydrogen-1H-azepan, 60 ℃ were stirred 5 hours down.Reaction mixture to be cooled pours into reaction mixture in the saturated aqueous ammonium chloride near after the room temperature, and mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.25g 1-(6-(2-butyne oxygen base) pyrimidine-4-yl)-anti--2,6-dimethyl-six hydrogen-1H-azepan (being called compound (43) hereinafter).
Figure A20048001247300541
1H-NMR：0.90(d，3H)，1.12(d，3H)，1.42-1.64(m，5H)，1.87(t，3H)，1.98-2.13(m，2H)，3.23(d，1H)，3.86-4.26(br，2H)，4.91(q，2H)，5.85(s，1H)，8.01(s，1H)
GC-MS：273(M+)
Production example 44
0.02g sodium hydride (60% oil suspension) is suspended in the 1ml tetrahydrofuran (THF).To the 0.3ml tetrahydrofuran solution that wherein drips 0.02g 2-butyne-1-alcohol, mixture stirred 10 minutes under the room temperature.Drip the 0.3ml tetrahydrofuran solution of 0.05g 6-chloro-4-(anti--3,5-lupetidine subbase)-5-fluorine pyrimidine under the room temperature in mixture, 60 ℃ were stirred 7 hours down.Reaction mixture to be cooled pours into reaction mixture in the saturated aqueous ammonium chloride near after the room temperature, and mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.05g 4-(2-butyne oxygen base)-6-(anti--3,5-lupetidine subbase) pyrimidine (being called compound (44) hereinafter).
Figure A20048001247300542
1H-NMR：0.95(d，6H)，1.49(t，2H)，1.87(t，3H)，1.94-2.03(m，2H)，3.32(dd，2H)，3.76(dd，2H)，4.97(q，2H)，8.02(s，1H)
Production example 45
0.2g 4-chloro-6-(valerylene oxygen base) pyrimidine mixes with 0.31g octahydro Azacyclooctane, places 2 hours under the room temperature.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.30g 1-(6-(2-butyne oxygen base) pyrimidine-4-yl) octahydro-1H-Azacyclooctane (being called compound (45) hereinafter).
Figure A20048001247300551
1H-NMR：1.44-1.58(m，6H)，1.70-1.78(m，4H)，1.87(t，3H)，3.56(brs，4H)，4.92(q，2H)，5.75(s，1H)，8.30(s，1H)
Production example 46
0.2g 4-(2-butyne oxygen base)-6-chloro-5-fluorine pyrimidine mixes with 0.34g octahydro Azacyclooctane, places 2 hours under the room temperature.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.28g 1-(6-(2-butyne oxygen base)-5-fluorine pyrimidine-4-yl) octahydro-1H-Azacyclooctane (being called compound (46) hereinafter).
1H-NMR：1.50-1.61(m，6H)，1.74-1.80(m，4H)，1.87(t，3H)，3.70(brt，4H)，4.97(q，2H)，8.03(s，1H)
Production example 47
0.07g sodium hydride (60% oil suspension) is suspended in the 2ml tetrahydrofuran (THF).To the 0.5ml tetrahydrofuran solution that wherein drips 0.10g 2-butyne-1-alcohol, mixture stirred 10 minutes under the room temperature.Drip the 0.5ml tetrahydrofuran solution of 0.20g 1-(6-chloro-5-fluorine pyrimidine-4-yl)-2-methyl-six hydrogen-1H-azepan under the room temperature in mixture, 60 ℃ were stirred 6 hours down.Reaction mixture to be cooled pours into reaction mixture in the saturated aqueous ammonium chloride near after the room temperature, and mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.27g 1-(6-(2-butyne oxygen base)-5-fluorine pyrimidine-4-yl)-2-methyl-six hydrogen-1H-azepan (being called compound (47) hereinafter).
Figure A20048001247300561
1H-NMR:1.16 (d, 3H), 1.18-1.45 (m, 3H), 1.60-1.89 (m, 7H comprise the triplet at 1.87 places), 2.03-2.12 (m, 1H), 3.05 (t, 1H), 3.99 (d, 1H), 4.48-4.59 (m, 1H), 4.97 (q, 2H), 8.02 (s, 1H)
Production example 48
0.06g sodium hydride (60% oil suspension) is suspended in the 1.5ml tetrahydrofuran (THF).To the 0.3ml tetrahydrofuran solution that wherein drips 0.08g 2-butyne-1-alcohol, mixture stirred 10 minutes under the room temperature.Drip the 0.3ml tetrahydrofuran solution of 0.19g 6-chloro-4-(suitable-the lupetidine subbase) pyrimidine under the room temperature in mixture, 60 ℃ were stirred 6 hours down.Reaction mixture to be cooled pours into reaction mixture in the saturated aqueous ammonium chloride near after the room temperature, and mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.20g 4-(2-butyne oxygen base)-6-(suitable-the lupetidine subbase) pyrimidine (being called compound (48) hereinafter).
Figure A20048001247300562
1H-NMR:1.20 (d, 6H), 1.51-1.57 (m, 1H), 1.62-1.75 (m, 4H), 1.82-1.89 (m, 4H comprise the triplet at 1.88 places), 4.50 (brs, 2H), 4.92 (q, 2H), 5.83 (s, 1H), 8.33 (s, 1H)
Production example 49
0.05g sodium hydride (60% oil suspension) is suspended in the 2ml tetrahydrofuran (THF).To the 0.3ml tetrahydrofuran solution that wherein drips 0.09g 2-butyne-1-alcohol, mixture stirred 10 minutes under the room temperature.Drip the 0.3ml tetrahydrofuran solution of 0.21g 6-chloro-4-(suitable-the lupetidine subbase)-5-fluorine pyrimidine under the room temperature in mixture, 60 ℃ were stirred 6 hours down.Reaction mixture to be cooled pours into reaction mixture in the saturated aqueous ammonium chloride near after the room temperature, and mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.21g 4-(2-butyne oxygen base)-6-(suitable-the lupetidine subbase)-5-fluorine pyrimidine (being called compound (49) hereinafter).
Figure A20048001247300571
1H-NMR:1.28 (d, 6H), 1.48-1.58 (m, 1H), 1.62-1.79 (m, 4H), 1.82-1.90 (m, 4H comprise the triplet at 1.87 places), 4.68-4.76 (m, 2H), 4.97 (q, 2H), 8.06 (s, 1H)
Production example 50
0.07g sodium hydride (60% oil suspension) is suspended in the 2ml tetrahydrofuran (THF).To the 0.3ml tetrahydrofuran solution that wherein drips 0.11g 2-butyne-1-alcohol, mixture stirred 10 minutes under the room temperature.Drip the 0.3ml tetrahydrofuran solution of 0.30g 1-(6-chloro-5-fluorine pyrimidine-4-yl)-2-ethyl-six hydrogen-1H-azepan under the room temperature in mixture, 60 ℃ were stirred 9 hours down.Reaction mixture to be cooled pours into reaction mixture in the saturated aqueous ammonium chloride near after the room temperature, and mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.31g 1-(6-(2-butyne oxygen base)-5-fluorine pyrimidine-4-yl)-2-ethyl-six hydrogen-1H-azepan (being called compound (50) hereinafter).
1H-NMR:0.88 (t, 3H), 1.18-1.88 (m, 12H comprise the triplet at 1.87 places), 2.14-2.21 (m, 1H), 3.01 (dd, 1H), 4.01 (br d, 1H), 4.51 (br s, 1H), 4.97 (q, 2H), 8.00 (s, 1H)
Production example 51
0.09g sodium hydride (60% oil suspension) is suspended in the 3ml tetrahydrofuran (THF).To the 0.3ml tetrahydrofuran solution that wherein drips 0.15g 2-butyne-1-alcohol, mixture stirred 10 minutes under the room temperature.In mixture, drip 0.40g 4 under the room temperature, the 0.3ml tetrahydrofuran solution of 5-two fluoro-6-(3,5-lupetidine subbase) pyrimidines (suitable/anti-diastereomer approximates 5/1), 0 ℃ was stirred 20 minutes down.Reaction mixture is poured in the saturated aqueous ammonium chloride, and mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.46g 4-(2-butyne oxygen base)-5-fluoro-6-(3,5-lupetidine subbase) pyrimidines (being called compound (51) hereinafter).Because two methyl are arranged on piperidine ring, compound (51) has suitable/anti-diastereomer.The ratio of suitable/anti-diastereomer is about 5/1.
Figure A20048001247300581
1H-NMR:0.80 (dd, 1H), 0.91 (d, 6H), 1.60-1.72 (m, 2H), 1.81-1.89 (m, 4H comprise the triplet at 1.87 places), 2.40 (dd, 2H), 4.39 (dd, 2H), 4.97 (q, 2H), 8.04 (s, 1H); 0.94 (s), 1.49 (t), 1.94-2.03 (m), 3.31 (dd), 3.75 (dd), 8.02 (s)
Production example 52
0.09g sodium hydride (60% oil suspension) is suspended in the 2ml tetrahydrofuran (THF).To the 0.3ml tetrahydrofuran solution that wherein drips 0.13g 2-butyne-1-alcohol, mixture stirred 10 minutes under the room temperature.In mixture, drip 0.40g 5-chloro-2 under 0 ℃, the 0.3ml tetrahydrofuran solution of 4-two fluoro-6-(3,5-lupetidine subbase) pyrimidine, uniform temp stirred 30 minutes down.Reaction mixture is poured in the saturated aqueous ammonium chloride, and mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.20g 5-chloro-4-(2-butyne oxygen base)-2-fluoro-6-(3,5-lupetidine subbase) pyrimidines (being called compound (52) hereinafter).Because two methyl are arranged on piperidine ring, compound (52) has suitable/anti-diastereomer.The ratio of suitable/anti-diastereomer is about 5/1.
Figure A20048001247300591
1H-NHR:0.79 (dd, 1H), 0.91 (d, 6H), 1.68-1.89 (m, 6H. comprise the triplet at 1.87 places), 2.40 (dd, 2H), 4.37 (dd, 2H), 4.97 (q, 2H) have the peak 0.96 (d) of less important isomer, 1.47 (t), 1.98-2.07 (m), 3.37 (dd), 3.68 (dd)
Production example 53
0.2g 4-(2-butyne oxygen base)-6-chloro-5-fluorine pyrimidine and 0.25g 1,2,3, the 6-tetrahydropyridine mixes, and places 3 hours under the room temperature.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.25g 1-(6-(2-butyne oxygen base)-5-fluorine pyrimidine-4-yl)-1,2,3,6-tetrahydropyridine (being called compound (53) hereinafter).
Figure A20048001247300592
1H-NMR：1.87(t，3H)，2.22-2.28(m，2H)，3.82(t，2H)，4.16-4.20(m，2H)，4.98(q，2H)，5.70-5.75(m，1H)，5.86-5.92(m，1H)，8.06(s，1H)
Production example 54
0.3g 4-chloro-6-(2-butyne oxygen base) pyrimidine and 0.41g 1,2,3, the 6-tetrahydropyridine mixes, and places 2 hours under the room temperature.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.38g 1-(6-(2-butyne oxygen base) pyrimidine-4-yl)-1,2,3,6-tetrahydropyridine (being called compound (54) hereinafter).
1H-NMR：1.87(t，3H)，2.18-2.25(m，2H)，3.76(t，2H)，3.90-3.94(m，2H)，4.93(q，2H)，5.72-5.78(m，1H)，5.83(s，1H)，5.89-5.96(m，1H)，8.33(s，1H)
Production example 55
0.3g 4-chloro-6-(2-amylene oxygen base) pyrimidine and 0.25g 1,2,3, the 6-tetrahydropyridine mixes, and places 3 hours under the room temperature.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.23g 1-(4-(valerylene oxygen base) pyrimidine-6-yl) pyridine (being called compound (55) hereinafter).
Figure A20048001247300602
1H-NMR：1.07(t，3H)，2.13-2.20(m，4H)，3.68(t，2H)，3.82-3.85(m，2H)，4.86(t，2H)，5.63-5.69(m，1H)，5.73(s，1H)，5.81-5.86(m，1H)，8.23(s，1H)
Next, the production of The compounds of this invention intermediate will be illustrated as with reference to production example.
With reference to production example 1
0.61g sodium hydride (60% oil suspension) is suspended in the 20ml tetrahydrofuran (THF).To the 1ml tetrahydrofuran solution that wherein drips 0.73g 2-butyne-1-alcohol, mixture stirred 10 minutes under 0 ℃.In mixture, drip 1.75g 4, the 5ml tetrahydrofuran solution of 6-two chloro-5-fluorine pyrimidines, 0 ℃ was stirred 90 minutes down.Reaction mixture is poured in the saturated aqueous ammonium chloride, and mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 1.8g 4-(2-butyne oxygen base)-6-chloro-5-fluorine pyrimidine.
Figure A20048001247300611
1H-NMR：1.79(t，3H)，5.00(q，2H)，8.29(s，1H)
With reference to production example 2
1.05g sodium hydride (60% oil suspension) is suspended in the 24ml tetrahydrofuran (THF).To the 8ml tetrahydrofuran solution that wherein slowly drips 1.42g 2-butyne-1-alcohol, mixture stirred 20 minutes under the room temperature.Slowly drip 3g 4 under 0 ℃ in mixture, the 8ml tetrahydrofuran solution of 6-dichloro pyrimidine stirred 4 hours.Reaction mixture is poured in the saturated aqueous ammonium chloride mixture chloroform extraction 3 times.Organic phase washes with water, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 3.16g 4-chloro-6-(2-butyne oxygen base) pyrimidine.
Figure A20048001247300612
Mp：43.5℃。
With reference to production example 3
0.56g sodium hydride (60% oil suspension) is suspended in the 18ml tetrahydrofuran (THF).To the 2ml tetrahydrofuran solution that wherein slowly drips 0.8g 2-butyne-1-alcohol, mixture stirred 20 minutes under the room temperature.Slowly drip 3g 4,5 under 0 ℃ in mixture, the 5ml tetrahydrofuran solution of 6-trichloropyrimidine stirred 2 hours.Reaction mixture is poured in the saturated aqueous ammonium chloride mixture ethyl acetate extraction 3 times.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 2.23g 4,5-two chloro-6-(2-butyne oxygen base) pyrimidine.
Figure A20048001247300613
1H-NMR：1.88(t，3H)，5.08(q，2H)，8.48(s，1H)
With reference to production example 4
0.32g sodium hydride (60% oil suspension) is suspended in the 12ml tetrahydrofuran (THF).To the 2ml tetrahydrofuran solution that wherein slowly drips 0.43g 2-butyne-1-alcohol, mixture stirred 20 minutes under the room temperature.Slowly drip 1g 4 under 0 ℃ in mixture, the 2ml tetrahydrofuran solution of 6-two chloro-5-methylpyrimidines stirred 2 hours.Reaction mixture is poured in the saturated aqueous ammonium chloride, and mixture extracts 3 times with t-butyl methyl ether.Organic phase washes with water, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 1.1g 4-chloro-6-(2-butyne oxygen base)-5-methylpyrimidine.
1H-NMR：1.88(t，3H)，2.26(s，3H)，5.00(q，2H)，8.44(s，1H)
With reference to production example 5
0.58g sodium hydride (60% oil suspension) is suspended in the 20ml tetrahydrofuran (THF).To the 1ml tetrahydrofuran solution that wherein slowly drips 0.88g valerylene-1-alcohol, mixture stirred 10 minutes under 0 ℃.Slowly drip 2g 4 under 0 ℃ in mixture, the 5ml tetrahydrofuran solution of 6-two chloro-5-fluorine pyrimidines stirred 70 minutes.Reaction mixture is poured in the saturated aqueous ammonium chloride, and mixture extracts 3 times with t-butyl methyl ether.Organic phase washes with water, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 2.31g 4-chloro-5-fluoro-6-(valerylene oxygen base) pyrimidine.
Figure A20048001247300622
1H-NMR：1.15(t，3H)，2.24(qt，2H)，5.09(t，2H)，8.36(s，1H)
With reference to production example 6
0.3g 4,6-dichloro pyrimidine and 0.34g 3,5-lupetidine (suitable/anti-diastereomer approximates 3/1) mixes, and places 5 hours under the room temperature.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.3g 4-chloro-6-(3,5-lupetidine subbase) pyrimidine.Because two methyl are arranged on the piperidine ring, this compound has suitable/anti-diastereomer.The ratio of suitable/anti-diastereomer is about 3.1/1.
1H-NMR：0.85(dd，1H)，0.95(d，6H)，1.56-1.68(m，2H)，1.84-1.89(m，1H)，2.37(dd，2H)，6.49(s，1H)，8.34(s，1H)；0.95(d)，1.90-2.25(m)，3.20-3.31(m)3.59-3.76(m)，6.47(s)，8.32(s)
With reference to production example 7
0.2g 4,6-two chloro-5-fluorine pyrimidine and 0.41g 3,5-lupetidine (suitable/anti-diastereomer approximates 3/1) mixes, and places 30 minutes under the room temperature.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.1g 4-chloro-6-(suitable-3,5-lupetidine subbase)-5-fluorine pyrimidine and 0.05g 4-chloro-6-(anti--3,5-lupetidine subbase) pyrimidine.
Figure A20048001247300632
The cis diastereomer:
1H-NMR：0.84(dd，1H)，0.93(d，6H)，1.64-1.78(m?，2H)，1.84-1.92(m，1H)，2.46(dd，2H)，4.48(d，2H)，8.11(s，1H)
Trans diastereomer:
1H-NMR：0.96(d，6H)，1.51(t，2H)，1.96-2.06(m，2H)，3.40(dd，2H)，3.83(dd，2H)，8.10(s，1H)
With reference to production example 8
0.07g sodium hydride (60% oil suspension) is suspended in the 3ml tetrahydrofuran (THF).To the 1ml tetrahydrofuran solution that wherein slowly drips 0.14g 2-ethyl piperidine, mixture stirred 10 minutes under the room temperature.Drip 0.2g 4 under the room temperature in mixture, the 1ml tetrahydrofuran solution of 6-two chloro-5-fluorine pyrimidines stirred 4 hours.Reaction mixture is poured in the saturated aqueous ammonium chloride, and mixture extracts 3 times with t-butyl methyl ether.Organic phase washes with water, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.22g 4-chloro-6-(2-ethyl piperidine subbase)-5-fluorine pyrimidine.
Figure A20048001247300641
1H-NMR：0.89(t，3H)，1.50-1.76(m，7H)，1.78-1.91(m，1H)，3.08(td，1H)，4.35-4.42(m，1H)，4.54-4.62(m，1H)，8.10(s，1H)
With reference to production example 9
0.2g 4,6-dichloro pyrimidine, 0.56g salt of wormwood and 0.26g hydrochloric acid 2,5-dimethyl six hydrogen-1H-azepan joins in the 3ml acetonitrile, stirs the mixture 3 hours under 80 ℃.Reaction mixture is extremely near room temperature, and to wherein adding saturated aqueous ammonium chloride, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.3g 1-(6-chloropyrimide-4-yl)-2,5-dimethyl six hydrogen-1H-azepan.
Figure A20048001247300642
1H-NMR：0.84-2.10(m，13H)，2.98(brt，0.4H)，3.22-3.34(m，1.2H)，3.60-3.72(m，0.4H)，4.29(brd，0.4H)，4.71-4.83(m，0.6H)，6.36(s，0.6H)，6.44(s，0.4H)，8.36(s，1H)GC-MS：239(M+)
With reference to production example 10
0.2g 4,6-two chloro-5-fluorine pyrimidines, 0.50g salt of wormwood and 0.24g hydrochloric acid 2,5-dimethyl six hydrogen-1H-azepan joins in the 3ml acetonitrile, stirs the mixture 5 hours under 80 ℃.Reaction mixture is extremely near room temperature, and to wherein adding saturated aqueous ammonium chloride, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.3g 1-(6-chloro-5-fluorine pyrimidine-4-yl)-2,5-dimethyl six hydrogen-1H-azepan.
Figure A20048001247300651
1H-NMR:0.84-1.59 (m, 10H comprise the bimodal of 0.92 place), 1.66-1.71 (m, 1H), 1.84-1.92 (m, 1H), 2.05 (ddd, 1H), 3.16 (brt, 1H), 3.96 (br, 1H), 4.58 (br, 1H), 8.11 (s, 1H)
GC-MS：257(M+)
With reference to production example 11
0.3g 4,6-dichloro pyrimidine, 0.83g salt of wormwood and 0.43g hydrochloric acid are suitable-2,6-dimethyl six hydrogen-1H-azepan joins in the 4ml acetonitrile, stirs the mixture 4 hours under 60 ℃.Reaction mixture is extremely near room temperature, and to wherein adding saturated aqueous ammonium chloride, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 03g 1-(6-chloropyrimide-4-yl)-suitable-2,6-dimethyl six hydrogen-1H-azepan.
1H-NMR：0.92-2.13(m，13H)，2.71(dd，0.4H)，2.98-3.09(m，1.2H)，3.60-3.69(m，0.4H)，4.06(d，0.4H)，4.74-4.85(m，0.6H)，6.25(s，0.6H)，6.40(s，0.4H)，8.35(s，1H)
GC-MS：239(M+)
With reference to production example 12
0.2g 4,6-two chloro-5-fluorine pyrimidines, 0.50g salt of wormwood and 0.27g hydrochloric acid are suitable-2,6-dimethyl six hydrogen-1H-azepan joins in the 3ml acetonitrile, stirs the mixture 2 hours under 60 ℃.Reaction mixture is extremely near room temperature, and to wherein adding saturated aqueous ammonium chloride, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.3g 1-(6-chloro-5-fluorine pyrimidine-4-yl)-suitable-2,6-dimethyl six hydrogen-1H-azepan.
Figure A20048001247300661
1H-NMR:0.90-1.04 (m, 4H comprise the bimodal of 0.95 place), and 1.10-1.32 (m, 4H), 1.36-1.48 (m, 1H), 1.71-1.90 (m, 3H), 2.04-2.14 (m, 1H), 2.91 (brt, 1H), 3.70 (brs, 1H), 4.42-4.82 (br, and 1H) 8.09 (d, 1H)
GC-MS：257(M+)
With reference to production example 13
0.2g 4,6-two chloro-5-fluorine pyrimidines, 0.50g salt of wormwood and 0.27g hydrochloric acid are anti--2,6-dimethyl six hydrogen-1H-azepan joins in the 3ml acetonitrile, stirs the mixture 2 hours under 60 ℃.Reaction mixture is extremely near room temperature, and to wherein adding saturated aqueous ammonium chloride, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.31g 1-(6-chloro-5-fluorine pyrimidine-4-yl)-anti--2,6-dimethyl six hydrogen-1H-azepan.
Figure A20048001247300671
1H-NMR：0.92(d，3H)，1.19(d，3H)1.44-1.65(m，5H)，1.94-2.11(m，2H)，3.41(d，1H)，4.17(brd，1H)，4.47-4.56(m，1H)8.10(d，1H)
With reference to production example 14
0.2g 4,6-dichloro pyrimidine, 0.56g salt of wormwood and 0.31g hydrochloric acid are anti--2,6-dimethyl six hydrogen-1H-azepan joins in the 3ml acetonitrile, stirs the mixture 2 hours under 60 ℃.Reaction mixture is extremely near room temperature, and to wherein adding saturated aqueous ammonium chloride, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.30g 1-(6-chloropyrimide-4-yl)-anti--2,6-dimethyl six hydrogen-1H-azepan.
1H-NMR：0.91(d，3H)，1.14(d，3H)1.42-1.68(m，7H)，2.04(ddd，1H)，2.10-2.18(m，1H)，3.26(brs，1H)，6.47(s，1H)8.33(s，1H)
GC-MS：239(M+)
With reference to production example 15
To 0.5g 2,4, drip 0.34g 3 in the 6ml tetrahydrofuran solution of 6-three fluoro-5-chloropyrimide under the room temperature, 5-lupetidine (suitable/anti-diastereomer approximates 4/1) stirred the mixture under the same temperature 1.5 hours.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.56g 5-chloro-2,4-two fluoro-6-(3,5-lupetidine subbase) pyrimidine.Because two methyl are arranged on the piperidine ring, this compound has suitable/anti-diastereomer.The ratio of suitable/anti-diastereomer is about 5/1.
1H-NMR:0.87 (dd, 1H), 0.94 (d, 6H), 1.70-1.82 (m, 2H), 1.86-1.94 (m, 1H), 2.47 (dd, 2H), 4.56 (dd 2H) has the peak 0.97 (d) of less important isomer, 1.51 (t), 2.02-2.11 (m), 3.51 (dd) .3.82 (dd)
With reference to production example 16
5g 2, and 6-dimethylcyclohexanon and 5.51g oxammonium hydrochloride are suspended in the 80ml ethanol, and 0 ℃ drips the 9.4g pyridine down, stirred the mixture under the room temperature 4 hours.Concentrated reaction mixture, water join in the resistates, mixture ethyl acetate extraction 3 times.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, and it is suitable-2 to obtain 1.3g, and 6-dimethylcyclohexanon oxime and 1.3g are anti--2,6-dimethylcyclohexanon oxime.
Figure A20048001247300682
The cis diastereomer:
1H-NMR：1.19(d，3H)，1.21(d，3H)，1.42-1.51(m，1H)，1.53-1.85(m，5H)，2.58-2.67(m，1H)，3.39-3.48(m，1H)，8.58(brs，1H)
Figure A20048001247300683
Trans diastereomer:
1H-NMR：1.08(d，3H)，1.12(d，3H)，1.14-1.25(m，1H)，1.52-1.72(m，4H)，1.83-1.91(m，1H)，2.32-2.46(m，1H)，3.64-3.69(m，1H)，8.81(s，1H)
With reference to production example 17
3.1g suitable-2,6-dimethylcyclohexanon oxime and 12g Tripyrophosphoric acid join in the 40ml dimethylbenzene, stir the mixture 10 hours under 100 ℃.Reaction mixture pours in the frozen water near room temperature.In this mixture, add yellow soda ash, mixture ethyl acetate extraction 3 times.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, and it is suitable-3 to obtain 2.5g, 7-dimethyl six hydrogen-1H-nitrogen heterocyclic heptan-2-ketone.
Figure A20048001247300691
1H-NMR：1.31(d，3H)，1.91(d，3H)，1.26-1.36(m，1H)，1.40-1.51(m，1H)，1.60-1.76(3H)，1.91-1.97(m，1H)，2.48-2.56(m，1H)，3.49-3.58(m，1H)，5.36(brs，1H)
With reference to production example 18
0.54g lithium aluminum hydride is suspended in the 20ml tetrahydrofuran (THF), and is suitable-3 to wherein adding 1g gradually under 0 ℃, in 7-dimethyl six hydrogen-1H-nitrogen heterocyclic heptan-2-ketone, the mixture reflux conditions stirred 10 hours down.Reaction mixture to 0 ℃, successively to wherein adding 0.54ml water, 0.54ml 15% aqueous sodium hydroxide solution and 1.62ml water, mixture stirred 30 minutes subsequently.In mixture, add sal epsom, filter through Celite.In filtrate, add 8.4ml1N hydrogenchloride/diethyl ether under 0 ℃, stirred the mixture 1 hour, concentrate that to obtain 1g hydrochloric acid suitable-2,6-dimethyl six hydrogen-1H-azepan.
Figure A20048001247300692
1H-NMR：1.01(d，3H)，1.21-1.33(m，1H)，1.48(d，3H)，1.60-1.72(m，2H)，1.79-2.01(m，3H)，2.12-2.21(m，1H)，2.77-2.88(m，1H)，3.22(brd，1H)，3.54(brs，1H)，9.44(br，2H)
With reference to production example 19
1.3g anti--2,6-dimethylcyclohexanon oxime and 6g Tripyrophosphoric acid join in the 20ml dimethylbenzene, stir the mixture 10 hours under 100 ℃.Reaction mixture pours in the frozen water near room temperature.In this mixture, add yellow soda ash, mixture ethyl acetate extraction 3 times.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, and it is anti--3 to obtain 1.2g, 7-dimethyl six hydrogen-1H-nitrogen heterocyclic heptan-2-ketone.
Figure A20048001247300701
1H-NMR：1.21(d，3H)，1.25(d，3H)，1.43-1.63(m，2H)，1.76(brs，4H)，2.70-2.79(m，1H)，3.51-3.62(m，1H)，5.71(brs，1H)
With reference to production example 20
0.54g lithium aluminum hydride is suspended in the 20ml tetrahydrofuran (THF), and is anti--3 to wherein adding 1g gradually under 0 ℃, in 7-dimethyl six hydrogen-1H-nitrogen heterocyclic heptan-2-ketone, the mixture reflux conditions stirred 10 hours down.Reaction mixture to 0 ℃, successively to wherein adding 0.54ml water, 0.54ml 15% aqueous sodium hydroxide solution and 1.62ml water, mixture stirred 30 minutes subsequently.In mixture, add sal epsom, filter through Celite.In filtrate, add 8.4ml 1N hydrogenchloride/diethyl ether under 0 ℃, stirred the mixture 1 hour, concentrate that to obtain 0.98g hydrochloric acid anti--2,6-dimethyl six hydrogen-1H-azepan.
1H-NMR：0.98(d，3H)，1.27-1.39(m，1H)，1.53(d，3H)，1.65-1.75(m，1H)，1.81-1.99(m，4H)，2.42(brs，1H)，2.56-2.66(m，1H)，3.30-3.41(m，2H)，9.06(brs，1H)，9.62(br，1H)
With reference to production example 21
160 ℃ are stirred 10g 2, the mixture of 2-dimethylated pentanedioic acid and 37.5g urea 8 hours down.Add water under 100 ℃ in this reaction mixture, cooling mixture is extremely near room temperature.Ethyl acetate extraction 3 times of this mixture.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 7.6g 3,3-lupetidine-2,6-diketone.
Figure A20048001247300711
1H-NMR：1.29(s，6H)，1.83-1.88(m，2H)，2.64-2.68(m，2H)，7.94(brs，1H)
With reference to production example 22
0.54g lithium aluminum hydride is suspended in the 15ml tetrahydrofuran (THF), under 0 ℃ to wherein adding 1g 3 gradually, 3-lupetidine-2, the 6-diketone, the mixture reflux conditions stirred 10 hours down.Reaction mixture to 0 ℃, successively to wherein adding 0.54ml water, 0.54ml 15% aqueous sodium hydroxide solution and 1.61ml water, mixture stirred 30 minutes subsequently.In mixture, add sal epsom, filter through Celite.In filtrate, add 10.6ml1N hydrogenchloride/diethyl ether under 0 ℃, stirred the mixture 1 hour, concentrate and obtain 0.7g hydrochloric acid 3,3-lupetidine.
Figure A20048001247300712
1H-NMR：1.12(s，6H)，1.45-1.48(m，2H)，1.84-1.91(m，2H)，2.85(brs，2H)，3.09(brs，2H)，9.31(br，2H)
With reference to production example 23
160 ℃ are stirred 5g 2, the mixture of 3-dimethyl succinate and 20g urea 10 hours down.Add water under 100 ℃ in this reaction mixture, cooling mixture is extremely near room temperature.Ethyl acetate extraction 3 times of this mixture.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 4.7g 3,4-dimethyl pyrrolidine-2, the suitable/anti-non-enantiomer mixture of 5-diketone.
Figure A20048001247300721
1H-NMR：1.24(d，1.2H)，1.35(d，4.8H)，2.45-2.53(m，1.6H)，2.95-3.04(m，0.4H)8.01(br，1H)
With reference to production example 24
1.19g lithium aluminum hydride is suspended in the 15ml tetrahydrofuran (THF), under 0 ℃ to wherein adding 1g 3 gradually, 4-dimethyl pyrrolidine-2, the 5-diketone, the mixture reflux conditions stirred 10 hours down.Reaction mixture to 0 ℃, successively to wherein adding 1.2ml water, 1.2ml15% aqueous sodium hydroxide solution and 3.6ml water, mixture stirred 30 minutes subsequently.In mixture, add sal epsom, filter through Celite.In filtrate, add 9.44ml1N hydrogenchloride/diethyl ether under 0 ℃, stirred the mixture 1 hour, concentrate and obtain 0.62g hydrochloric acid 3, the suitable/anti-non-enantiomer mixture of 4-dimethyl pyrrolidine.
Figure A20048001247300722
1H-NMR：1.01(d，1.2H)，1.08(d，4.8H)，1.79-1.91(m，1.6H)，2.36-2.43(m，0.4H)，2.83(dd，1.6H)，2.97(dd，0.4H)，3.41(dd，0.4H)，3.52(dd，1.6H)，6.52(br，1H)
With reference to production example 25
160 ℃ of mixtures that stir down 2.6g tetramethyl-pentanedioic acid and 8.3g urea 10 hours.Add water under 100 ℃ in this reaction mixture, cooling mixture is extremely near room temperature.Ethyl acetate extraction 3 times of this mixture.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 2.3g 3,3,5,5-tetramethyl piperidine-2,6-diketone.
Figure A20048001247300731
1H-NMR：1.31(s，12H)，1.81(s，2H)，7.75(br，1H)
Reference example 26
0.90g lithium aluminum hydride is suspended in the 13ml tetrahydrofuran (THF), under 0 ℃ to wherein adding 1g 3,3,5 gradually, 5-tetramethyl piperidine-2, the 6-diketone, the mixture reflux conditions stirred 10 hours down.Reaction mixture to 0 ℃, successively to wherein adding 0.9ml water, 0.9ml15% aqueous sodium hydroxide solution and 2.7ml water, mixture stirred 30 minutes subsequently.In mixture, add sal epsom, filter through Celite.In filtrate, add 7ml 1N hydrogenchloride/diethyl ether under 0 ℃, stirred the mixture 1 hour, concentrate and obtain 0.59g hydrochloric acid 3,3,5,5-tetramethyl piperidine.
Figure A20048001247300732
1H-NMR：1.71(s，12H)，1.97(brs，2H)，2.81-2.84(m，4H)，9.49(br，2H)
With reference to production example 27
160 ℃ are stirred 10g 3, the mixture of 3-dimethyl succinate and 102.7g urea 10 hours down.Add water under 100 ℃ in this reaction mixture, cooling mixture is extremely near room temperature.Ethyl acetate extraction 3 times of this mixture.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 7.8g 3,3-dimethyl pyrrolidine-2,5-diketone.
1H-NMR：1.35(s，6H)，2.60(s，2H)，8.36(br，1H)
With reference to production example 28
0.96g lithium aluminum hydride is suspended in the 15ml tetrahydrofuran (THF), under 0 ℃ to wherein adding 1g 3 gradually, 3-dimethyl pyrrolidine-2, the 5-diketone, the mixture reflux conditions stirred 12 hours down.Reaction mixture to 0 ℃, successively to wherein adding 0.96ml water, 0.96ml 15% aqueous sodium hydroxide solution and 2.88ml water, mixture stirred 30 minutes subsequently.In mixture, add sal epsom, filter through Celite.In filtrate, add 15.74ml 1N hydrogenchloride/diethyl ether under 0 ℃, stirred the mixture 1 hour, concentrate and obtain 0.45g hydrochloric acid 3,3-dimethyl pyrrolidine.
1H-NMR：1.19(s，6H)，1.79-1.84(m，2H)，3.01-3.07(m，2H)，3.43-3.51(m，2H)，9.37(br，2H)
With reference to production example 29
0.4g 4,6-two chloro-5-fluorine pyrimidines and 0.61g 2-ethyl six hydrogen-1H-azepan mixes, and places 1 hour under the room temperature.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.6g1-(6-chloro-5-fluorine pyrimidine-4-yl)-2-ethyl six hydrogen-1H-azepan.
Figure A20048001247300743
1H-NMR：0.90(t，3H)，1.16-1.41(m，3H)，1.48-1.68(m，3H)，1.78-1.83(m-3H)，2.17-2.24(m，1H)，3.07(br?t，1H)，4.08(brs，1H)，4.40-4.80(br，1H)，8.09(s，1H)
With reference to production example 30
0.5g 4,6-dichloro pyrimidine and 0.76g be suitable-and lupetidine mixes, and 90 ℃ were stirred 10 hours down.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.21g 4-chloro-6-(suitable-the lupetidine subbase) pyrimidine.
Figure A20048001247300751
1H-NMR：1.23(d，6H)，1.55-1.59(m，1H)，1.67-1.73(m，4H?)，1.82-1.90(m，1H)，4.48-4.65(br，2H)，6.44(s，1H)，8.38(s，1H)
With reference to production example 31
0.25g 4,6-two chloro-5-fluorine pyrimidines and 0.34g be suitable-and lupetidine mixes, and 70 ℃ were stirred 11 hours down.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.21g 4-chloro-6-(suitable-the lupetidine subbase)-5-fluorine pyrimidine.
Figure A20048001247300752
1H-NMR：1.32(d，6H)，1.53-1.58(m，1H)，1.67-1.81(m，4H)，1.82-1.94(m，1H)，4.83(br?s，2H)，8.14(s，1H)
With reference to production example 32
0 ℃ of following 0.5g 4,5 drips 0.51g 3 in the 6ml toluene solution of 6-trifluoro pyrimidine, the 1ml toluene solution of 5-lupetidine (suitable/anti-diastereomer approximates 4/1) stirred the mixture under the same temperature 1.5 hours.Reaction mixture carries out the silica gel column chromatography chromatography, obtains 0.83g4,5-two fluoro-6-(3,5-lupetidine subbase) pyrimidine.Because two methyl are arranged on the piperidine ring, this compound has suitable/anti-diastereomer.The ratio of suitable/anti-diastereomer is about 5/1.
1H-NMR:0.84 (dd, 1H), 0.94 (d, 6H), and 1.64-1.75 (m, 2H), 1.88 (br d, 1H), 2.46 (dd, 2H), and 4.46-4.51 (m, 2H), 8.02 (s 1H) has the peak 0.95 (d) of less important isomer, 1.52 (t), 1.96-2.08 (m), 3.39 (dd) .3.83 (dd), 8.00 (s)
With reference to production example 33
0.13g 4,6-two chloro-5-fluorine pyrimidines, 0.14g salt of wormwood and 0.10g hydrochloric acid 2-methyl six hydrogen-1H-azepan join in the 2ml acetonitrile, stir the mixture 2 hours under 60 ℃.Reaction mixture is extremely near room temperature, and to wherein adding saturated aqueous ammonium chloride, mixture extracts 3 times with t-butyl methyl ether.Organic phase is washed with saturated sodium-chloride water solution, and anhydrous magnesium sulfate drying concentrates.Resistates carries out the silica gel column chromatography chromatography, obtains 0.20g 1-(6-chloro-5-fluorine pyrimidine-4-yl)-2-methyl six hydrogen-1H-azepan.
Figure A20048001247300762
1H-NMR:1.17-1.50 (m, 6H comprise the bimodal of 1.18 places), 1.58-1.92 (m, 4H), 2.06-2.14 (m, 1H), 3.11 (t, 1H), 4.01 (brd, 1H), 4.57 (brs, 1H), 8.11 (s, 1H).
To show example of formulations below.Part is a weight part.
Example of formulations 1
Get each 9 parts of The compounds of this invention (1) to (51), be dissolved in 37.5 parts of dimethylbenzene and 37.5 parts of dimethyl formamides, to wherein adding 10 parts of polyoxyethylene vinylbenzene phenyl ethers (polyoxyethylene styrylphenyl ether) and 6 parts of calcium dodecylbenzene sulphonates, thorough mixing obtains preparation.
Example of formulations 2
Get each 9 parts of The compounds of this invention (1) to (51), be mixed in the mixture of 4 parts of sodium laurates, 2 parts of calcium lignosulfonates, 20 parts of synthetic aqueous silicon dioxide fine powders and 65 parts of Celite, thorough mixing obtains preparation.
Example of formulations 3
Get each 3 parts of The compounds of this invention (1) to (51); be mixed in the mixture of 5 parts of synthetic aqueous silicon dioxide fine powders, 5 parts of Sodium dodecylbenzene sulfonatees, 30 parts of wilkinites and 57 parts of clays; thorough mixing; the water that in mixture, adds appropriate amount then; continue to stir final mixture; granulate in nodulizer, air seasoning obtains preparation.
Example of formulations 4
Get each 4.5 parts of The compounds of this invention (1) to (51), in mortar with 1 part of synthetic aqueous silicon dioxide fine powder, 1 part of DRILESS B (Sankyo Co., Ltd. make) and the mixture thorough mixing of 7 parts of clays, (juice mixer) mixes through the juice stirrer.In final mixture, add 86.5 parts of engraving clays (cut clay), fully mix, obtain preparation.
Example of formulations 5
Get each 10 parts of The compounds of this invention (1) to (51), contain the white carbon ink of 50 parts of sulfuric acid Voranol EP 2001s with 35 parts, 55 parts of water mix, levigate fully by wet grinding, the acquisition preparation.
The effect that will show then, the The compounds of this invention pest control by experimental example.
Experimental example 1
It is 500ppm that the preparation of the test compound that obtains in the example of formulations 5 is diluted with water to effective constituent concentration, makes the test spraying liquid.
Cucumber seeds is planted in the polyethylene cup, and grow to and grow first trophophyll, parasitic about 20 cotton aphids (Aphis gossypii) on trophophyll.After one day, the ratio of test spraying liquid with the 20ml/ cup sparged on the cucumber plant.The number of cotton aphid is checked in after using the 6th day, measures the control value through following formula:
Control value (%)=1-(Cb * Tai)/(Cai * Tb) } * 100
Wherein, the variable in the formula has following implication:
Cb: the insect number before handling in the untreated areas;
Cai: the insect number in the untreated areas when observing;
Tb: the insect number before handling in the treatment zone;
Tai: the insect number in the treatment zone when observing;
The result is, The compounds of this invention (1) to (8) and (10) to (55) have 90% or higher control value.
Use formula (A) compound to compare test with identical method.
Figure A20048001247300781
This compound is at Tetrahedron Letters, and No.26 obtains in the 3067-3070 page or leaf (1968) describing.Formula (A) compound has 29% or lower control value.
Experimental example 2
It is 500ppm that the preparation of each test compound that obtains in the example of formulations 5 is diluted with water to activity component concentration, makes the test spraying liquid.
Cucumber seeds is planted in the polyethylene cup, and produce, use the test spraying liquid in plant with the ratio of 20ml/ cup then to growing first trophophyll.After waiting to sparge liquid on the cucumber and doing, the excision rough leaf places on polyethylene cup (diameter 110mm) the usefulness filter paper (diameter 70mm) of water infiltration.The larva of 30 Frankliniella occidentalis (Frankliniellaoccidentalis) is discharged on the rough leaf, covers with the polyethylene cup.After 7 days, check the insect number of survival.
The result is, on the leaf with each processing of The compounds of this invention (4), (8) to (11), (23), (24), (26), (29), (32), (33), (44), (46), (47), (51), (52) and (53), the insect number of survival is 0.
Experimental example 3
The preparation dilute with water of each test compound that obtains according to example of formulations 5 is made the spraying liquid of test, and wherein effective constituent concentration is 500ppm.
The Caulis et Folium Brassicae capitatae seed is planted in the polyethylene cup, grow to and grow first trophophyll.Stay first trophophyll and excise other leaf.Some Bemisia argentifoliis (Bemisiaargentifolii) adult is released on the Caulis et Folium Brassicae capitatae plant, allows to lay eggs 24 hours.Thereby Caulis et Folium Brassicae capitatae plant 80 to 100 ovum of having an appointment were placed Caulis et Folium Brassicae capitatae 8 days in the greenhouse, the ratio of above-mentioned test spraying liquid with the 20ml/ cup were sparged on the Caulis et Folium Brassicae capitatae plant of larva the ovum hatching of described larva from being produced.The larva number of survival is calculated in after using the 7th day.
The result is that to (53), the larva number of surviving on the Caulis et Folium Brassicae capitatae leaf with every kind of these compound treatment is no more than 10 for The compounds of this invention (1).
Experimental example 4
The concentration that the preparation of the test compound that obtains in the example of formulations 5 is diluted with water to test effect composition is 500ppm, makes the test spraying liquid.
50g earthing Bonsoru 2 (available from Sumitomo Chemical Co., Ltd.) is placed the polyethylene cup, 10-15 grain rice paddy seed is planted in the polyethylene cup.Paddy growth is cut into the sustained height of 5cm then to growing second trophophyll.To sparge on these rice plants with the ratio of 20ml/ cup as the above-mentioned obtained spraying liquid of must testing.After waiting to sparge the experimental liquid soma on the paddy rice, the first-instar youngs of 30 brown paddy plant hoppers (Nilaparvata lugens) is discharged on the rice plant, is positioned over then in 25 ℃ of greenhouses.Discharge the 6th day behind the brown paddy plant hopper larva, detect the brown paddy plant hopper number that colonizes on the rice plant.
The result is, with each treated water rice of The compounds of this invention (2), (3), (6), (10) to (12), (14), (15), (17), (18), (22) to (26), (30), (31), (33) to (35), (41) to (43), (45) to (49) and (51), the number of the 6th day parasitic insect after handling is no more than 3.
Industrial applicibility
The compounds of this invention has the ability of outstanding pest control, and therefore, it can be used as Active ingredient is used for pests controlling composition.

Claims (16)

1. the pyrimidine compound of a formula (I):
R wherein 1Expression hydrogen atom, halogen atom or C1-C4 alkyl; R 2Expression C3-C7 alkynyloxy group; R 3Expression hydrogen atom, halogen atom or C1-C3 alkyl; X represents the C4-C7 polymethylene, wherein can replace CH with CH=CH 2-CH 2, described polymethylene is selected from optional replacement of substituting group of halogen atom, trifluoromethyl and C1-C4 alkyl by at least one.
2. the pyrimidine compound of claim 1, wherein X is the optional C4-C7 polymethylene that replaces of the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one.
3. the pyrimidine compound of claim 1, wherein X is by the optional C4-C7 polymethylene that replaces of halogen atom, trifluoromethyl and C1-C4 alkyl.
4. the pyrimidine compound of claim 1, wherein X is the C4-C7 polymethylene.
5. the pyrimidine compound of claim 1, wherein the C4-C7 polymethylene of X for being replaced by halogen atom.
6. the pyrimidine compound of claim 1, wherein the C4-C7 polymethylene of X for being replaced by trifluoromethyl.
7. the pyrimidine compound of claim 1, wherein the C4-C7 polymethylene of X for being replaced by the C1-C4 alkyl.
8. the pyrimidine compound of claim 1, wherein X is by the linear alkenylene of the optional C4-C7 that replaces of halogen atom, trifluoromethyl and C1-C4 alkyl.
9. each pyrimidine compound of claim 1-8, wherein R 1Be hydrogen atom or C1-C4 alkyl.
10. each pyrimidine compound of claim 1-8, wherein R 2Be 2-butyne oxygen base or valerylene oxygen base.
11. a pests controlling composition, described composition comprise the pyrimidine compound of claim 1 as effective ingredient.
1 2. a kind of method of pest control, described method comprises the habitat that the pyrimidine compound of the claim 1 of significant quantity is applied to insect or insect.
13. the pyrimidine compound of a formula (II):
Figure A2004800124730003C1
Wherein, R 1Expression hydrogen atom, halogen atom or C1-C4 alkyl; R 3Expression hydrogen atom, halogen atom or C1-C3 alkyl; X 3Expression C4-C7 polymethylene wherein can be replaced CH with CH=CH 2-CH 2, described polymethylene is replaced by the substituting group that at least one is selected from halogen atom, trifluoromethyl and C1-C4 alkyl.
14. the pyrimidine compound of claim 1, wherein X 3The C4-C7 polymethylene that replaces for the substituting group that is selected from halogen atom, trifluoromethyl and C1-C4 alkyl by at least one.
15. the pyrimidine compound of claim 1, wherein X 3Be the C4-C7 polymethylene that is replaced by halogen atom.
16. the pyrimidine compound of claim 1, wherein X 3Be the C4-C7 polymethylene that is replaced by trifluoromethyl.
17. the pyrimidine compound of claim 1, wherein X 3Be the C4-C7 polymethylene that is replaced by the C1-C4 alkyl.
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